TW503514B - Film forming method, semiconductor device and semiconductor device manufacturing method - Google Patents

Film forming method, semiconductor device and semiconductor device manufacturing method Download PDF

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Publication number
TW503514B
TW503514B TW090117414A TW90117414A TW503514B TW 503514 B TW503514 B TW 503514B TW 090117414 A TW090117414 A TW 090117414A TW 90117414 A TW90117414 A TW 90117414A TW 503514 B TW503514 B TW 503514B
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Taiwan
Prior art keywords
film
insulating film
conductive wiring
protective layer
silicon
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TW090117414A
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Chinese (zh)
Inventor
Taizo Oku
Junichi Aoki
Youichi Yamamoto
Takashi Koromokawa
Kazuo Maeda
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Canon Sales Co Inc
Semiconductor Process Lab Co
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Application filed by Canon Sales Co Inc, Semiconductor Process Lab Co filed Critical Canon Sales Co Inc
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Publication of TW503514B publication Critical patent/TW503514B/en

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    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
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    • H01L21/314—Inorganic layers
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    • H01L21/31612—Deposition of SiO2 on a silicon body
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    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
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    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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    • H01L21/76831—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers in via holes or trenches, e.g. non-conductive sidewall liners
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
    • H01L21/76834—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers formation of thin insulating films on the sidewalls or on top of conductors
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    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract

The present invention relates to a film forming method of forming an interlayer insulating film having a low dielectric constant to cover a wiring. In construction, an insulating film for covering a wiring is formed on the substrate by plasmanizing a film forming gas, that consists of any one selected from a group consisting of alkoxy compound having Si-H bonds and siloxane having Si-H bonds and any one oxygen-containing gas selected from a group consisting of O2, N2O, NO2, CO, CO2, and H2O, to react.

Description

五、發明說明（1) 發明背景·· 1 ·發明領域 本發明是係有關於一種薄膜形成方法，半導體裝置及 半導體裝置之製造方法’具體地來說，一種薄膜形成方 法，半導體裝置及半導體裝置之製造方法，用來形成一具 低介電常數的層間絕緣膜，覆蓋在導電佈線上。 2 ·相關技術說明 近年來，由於半導體積體電路裝置在較高集積度和較 面费度的進步，因此微縮化與減少電路圖案厚度的要求被 提出來了。此外，增加資料傳輸率的要求也被提出了。 所以，具有低介電常數的層間絕緣膜（往後稱之為低 介電常數絕緣薄膜）以及因此延伸出來的小RC延遲（RC delay)被引用了。絕緣膜中，有相對介電常數約3β 5一3· 8 的Si OF膜，有介電常數約3· 0-3. 1多孔隙Si 02膜，等等， 舉例說明。 然而，非常重要地，低介電常數絕緣膜已經含有水氣 以及已經準備有水氣進入。所以假如這樣的低介電常數絕 緣膜被用來當作層間絕緣膜，則導電佈線的腐蝕以及漏電 流（Leakage current)的增力口是很容易發生的。 更具體地來說，有多層次的導電佈線，含有阻隔層的 層間絕緣膜，在上導電佈線以及下導電佈線之間被形成。 含有阻隔層的層間絕緣膜是將含有矽（S i )以及氮（N )，或矽（S i )和碳（C )的阻隔層，低介電常數絕緣V. Description of the invention (1) Background of the invention ... 1. Field of the invention The present invention relates to a thin film forming method, a semiconductor device, and a manufacturing method of a semiconductor device. In particular, a thin film forming method, a semiconductor device, and a semiconductor device The manufacturing method is used to form an interlayer insulating film with a low dielectric constant and cover the conductive wiring. 2 · Description of Related Technology In recent years, due to the advancement of semiconductor integrated circuit devices at higher integration levels and lower costs, requirements for miniaturization and reduction in circuit pattern thickness have been proposed. In addition, requests for increased data transmission rates have also been proposed. Therefore, an interlayer insulating film having a low dielectric constant (hereinafter referred to as a low dielectric constant insulating film) and a small RC delay extending therefrom are cited. Among the insulating films, there are Si OF films having a relative dielectric constant of about 3β 5 to 3. 8; there are porous Si 02 films having a dielectric constant of about 3.0 · 3.1; and the like, for example. However, it is very important that the low-dielectric-constant insulating film already contains water vapor and is ready to enter with water vapor. Therefore, if such a low-dielectric-constant insulating film is used as an interlayer insulating film, corrosion of the conductive wiring and a boost current of leakage current (Leakage current) can easily occur. More specifically, there are multiple layers of conductive wiring, and an interlayer insulating film including a barrier layer is formed between the upper conductive wiring and the lower conductive wiring. The interlayer insulating film containing a barrier layer is a low dielectric constant insulation layer that contains silicon (S i) and nitrogen (N), or a barrier layer of silicon (S i) and carbon (C)

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膜，以及含有矽（S i )以及g f w )的阻隔層依序分層疊入。 ，或矽（Si )和碳（c 常數。所以3 t ‘ it I皇以及氮（N )的阻隔層有高介電 吊默0所U，即使有較薄厚声沾 % 緣膜’整個層間絕緣膜的介；常U被用來备作阻隔絕 此外，含梦⑶）和；二數阳還是增加了。 為約5，大於含石夕（Si )):且隔絕緣膜的介電常數 含石夕（Si)和碳（C)的阻隔的阻隔絕緣膜’但是 電流的增加。 隔絕緣膜並不能有效地抑制漏 發明概述： 本發明的目的，是提供 置以及半導體裝置之製造方 的介電常數，以及抑制因為 當防止導電佈線腐蝕以及漏 的時候。 種薄膜形成方法，半導體裝 法’具備降低整個層間絕緣膜 水氣吸附而改變的介電常數， 電机（Leakage current)增加 如本發明之薄膜形成方法，含矽絕緣膜以e將彳h續暖 形成氣體所形成的，1中镇_ η緣膜以電漿化薄膜 個具有Si-H鍵之燒氧基形A1t氣體的组成’是任何一 ：Hr^r y^C〇mP^ Ω , N π Mn , r〇 有H鍵之裱乳矽氮烷（Siloxane)和 〇2 n2o，no2 co2，c〇AH2〇群組中 氣體，反應而成的。垠墟太審& ^ 似所選出的3乳 綾膜曰F ^，且古根據本實驗，發現到，這樣的含矽絕 緣膜疋厗的具巧防水氣，低介電常數。 所以彡&上述之含石夕絕緣膜被用纟當作P且隔絕緣膜The film and the barrier layer containing silicon (S i) and g f w) are sequentially laminated. , Or silicon (Si) and carbon (c constants. So the 3 t 'it I and nitrogen (N) barrier layer has a high dielectric susceptibility 0 U, even if there is a thin and thick acoustic coating% edge film' the entire interlayer insulation Membrane mediation; often U is used as a barrier isolation In addition, dreams (3) and; the number of yang is still increased. It is about 5, which is greater than that of Shi Xi (Si)): and the dielectric constant of the barrier film. Shi barrier (Si) and carbon (C) barrier barrier film ’but the current increases. Isolation of the edge film does not effectively suppress leakage. SUMMARY OF THE INVENTION The object of the present invention is to provide the dielectric constant of the device and the manufacturer of the semiconductor device, and to suppress the corrosion and leakage of conductive wiring when it is prevented. A method for forming a thin film, a semiconductor mounting method, which has a reduced dielectric constant that changes the moisture absorption of the entire interlayer insulating film. The motor (Leakage current) is increased as in the thin film forming method of the present invention. Formed by the warm forming gas, the composition of the 1_zhen η edge film is plasma-formed with a sintered oxygen-shaped A1t gas having a Si-H bond. It is any one: Hr ^ ry ^ C〇mP ^ Ω, N π Mn, r〇 H-bonded milking silazane (Siloxane) and 〇2 n2o, no2 co2, coOH2O group gas reaction. The Puxun Taishen & ^ resembled the selected 3 milk 绫 film called F ^, and according to this experiment, it was found that such a silicon-containing insulating film 具 has a smart waterproofness and a low dielectric constant. So 彡 & the above-mentioned stone-containing insulating film is used P as P and cut off the edge film

503514 五、發明說明（3) (上保護層以及下保護層），其組成為，將層間絕緣膜中 置在上導電佈線以及下導電佈線之間，夾層低介電常數的 絕緣膜，整個層間絕緣膜的介電常數可被降低，當防止導 電佈線腐蝕以及漏電流（Leakage current)增加的時候。 如本發明之半導體裝置，具有介於波數227 〇 —2 35〇cnri 的紅外線吸收強度峰值，薄膜密度範圍為 2· 25-2· 40g/cm3，和介電常數範圍為3· 3 —4· 3的含矽絕緣 膜是在基底上所形成。 如本發明之應用發名人的實驗，可發現到，具備如此 特徵的含矽絕緣薄膜有高機械強度，具厚度，極佳的防水 性’在膜中含有少量的水氣如氮化矽（s i N )膜，以及具 有比氮化矽（S i N )膜低的相對低介電常數。 ’、 如使用本發明的含矽絕緣膜至半導體裝置所獲得的建 構，上述含矽絕緣膜是被形成來覆蓋導電佈線以及與它接 觸，或者上述含矽絕緣膜是被形成當作在絕緣膜上用來覆 盖導電佈線的保護層。 本發明的含矽絕緣膜，具有低介電常數，在膜中含有 少量的水氣’具厚度’極佳的防水性。所以，如果含石夕絕 緣膜被用來覆蓋導電佈線的保護層，等，導電佈線的腐蝕 可在防止外來水氣進入半導體裝置的情況下被防止，當減 少介於導電佈線間的寄生電容時。 此外，上導電佈線，下導電佈線以及中置在上導電佈 線以及下導電佈線間的層間絕緣膜，在基底上被提供了， 以及層間絕緣膜是由如本發明的含矽絕緣膜所形成的。503514 V. Description of the invention (3) (upper protective layer and lower protective layer), which is composed of an interlayer insulating film placed between the upper conductive wiring and the lower conductive wiring, and an insulating film with a low dielectric constant is sandwiched between the entire layer. The dielectric constant of the insulating film can be reduced when the conductive wiring is prevented from being corroded and the leakage current is increased. For example, the semiconductor device of the present invention has an infrared absorption intensity peak at a wavenumber of 227 0-2 35 00cnri, a film density range of 2.25-2 · 40g / cm3, and a dielectric constant range of 3. · 3-4. · 3 silicon-containing insulating film is formed on the substrate. According to the experiments of the celebrities of the present invention, it can be found that the silicon-containing insulating film with such characteristics has high mechanical strength, thickness, and excellent water resistance. 'The film contains a small amount of water vapor such as silicon nitride (si N) film, and has a relatively low dielectric constant that is lower than that of a silicon nitride (SiN) film. '、 According to the structure obtained by using the silicon-containing insulating film of the present invention to a semiconductor device, the silicon-containing insulating film is formed to cover the conductive wiring and contact with it, or the silicon-containing insulating film is formed as an insulating film. A protective layer for covering conductive wiring. The silicon-containing insulating film of the present invention has a low dielectric constant, and contains a small amount of water vapor in the film 'with a thickness' and excellent waterproofness. Therefore, if a stone-containing insulating film is used to cover the protective layer of the conductive wiring, etc., the corrosion of the conductive wiring can be prevented without preventing the entry of external moisture into the semiconductor device. When reducing the parasitic capacitance between the conductive wiring . In addition, the upper conductive wiring, the lower conductive wiring, and the interlayer insulating film interposed between the upper conductive wiring and the lower conductive wiring are provided on the substrate, and the interlayer insulating film is formed of a silicon-containing insulating film such as the present invention. .

2060-4201-PF;nivek.ptd 第8頁 503514 五、發明說明（4) ^---- 此外，層間絕緣膜的組成依序是，從如本發明含矽絕 緣膜所形成的下保護層，主要絕緣膜，以及如本發明含矽 絕緣膜所形成的上保護層。 如果主要絕緣膜是以SiOF臈所形成，如本發明含矽絕 緣膜則可以防止氟（Flourine)元素擴散到含矽絕緣膜的外 周邊電路部分。此外，如果主要絕緣膜是由具高吸水氣性 的多孔隙絕緣膜所形成，如本發明含矽絕緣膜則可以防止 f氣進入多孔隙絕緣膜中並導致介電常數的增#，因為水 氣的吸附可以被防止。 此外，因為氮化矽（SiN)膜並未被使用來當作如果 主要絕緣膜的上以及下保護層，但是具有低介電常數的含 矽絕緣膜被使用，整個層間絕緣膜的介電常數可被減少。 圖式簡單說明： 第1圖係根據本發明第一實施例的薄膜形成方法中之 電漿CVD膜之形成設備側視圖。 第2A至2E圖展示出樣品的結構以及比較樣品，係根據 本發明第一實際例的薄膜形成方法所形成，用來檢視含矽 絕緣膜的特徵。 第3A至3B圖展示出係根據本發明第二實際例並利用樣 品2A的薄膜形成方法所形成的絕緣膜的薄膜密度檢視結 ,第4圖係根據本發明第二實際例並利用樣品2A的薄膜 形成方法所形成的含矽絕緣膜的抗水性以及水氣成分的檢2060-4201-PF; nivek.ptd Page 8 503514 V. Description of the invention (4) ^ ---- In addition, the composition of the interlayer insulating film is in order from the lower protective layer formed by the silicon-containing insulating film according to the present invention. , The main insulating film, and the upper protective layer formed by the silicon-containing insulating film according to the present invention. If the main insulating film is formed of SiOF, such as the silicon-containing insulating film of the present invention, it is possible to prevent fluorine (Flourine) elements from diffusing into the outer peripheral circuit portion of the silicon-containing insulating film. In addition, if the main insulating film is formed of a porous insulating film with high moisture absorption, such as the silicon-containing insulating film of the present invention, it is possible to prevent gas from entering the porous insulating film and cause an increase in dielectric constant because Adsorption of gas can be prevented. In addition, because a silicon nitride (SiN) film is not used as an upper and lower protective layer of a main insulating film, but a silicon-containing insulating film having a low dielectric constant is used, the dielectric constant of the entire interlayer insulating film Can be reduced. Brief description of the drawings: Fig. 1 is a side view of a plasma CVD film forming apparatus in a thin film forming method according to a first embodiment of the present invention. Figures 2A to 2E show the structure of the sample and the comparative sample, which were formed according to the thin film forming method of the first practical example of the present invention, for examining the characteristics of the silicon-containing insulating film. Figures 3A to 3B show the film density inspection results of an insulating film formed according to the second practical example of the present invention and using the thin film forming method of sample 2A. Figure 4 is a view of the second practical example of the present invention using the sample 2A. Detection of water resistance and moisture content of silicon-containing insulating film formed by film formation method

2060-4201 -PF;n i vek.p t d 五、發明說明（9) -- 鍵之％氧矽氮烷（Si l〇xane)的供應源，從，仏〇 , Μ%， C〇2 ’ CO ’ H2〇群組中任何一個所選出的含氧氣體所形成之 薄膜形成氣體，H2的供應源，％的供應源。 如Hs有Si Η鍵之燒氧基化合物（Aikoxyl compound) 或在本發明中被使用的，含有^咄鍵之環氧矽氮烷 (Si loxane)的薄膜形成氣體，接下來的將被當作典型的例 子來使用。 (Ο 3有Si-Η鍵之院氧基化合物（Aikoxyl compound) 二曱氧基石夕烧（Trimethoxysilane (TMS : SiH(0CH3)3)) (ii)Si-H鍵之環氧矽氮烷（si loxane) 4次甲基石夕氮烧（Tetramethylsiloxane ;TMDS0 : (CH3)2his - 0-SiH(CH3)2) 這些氣體在薄膜形成氣體供應區101A的反應室1中經 由支線9b-9f和支線9a所連接的地方被適當地供應。流率 調整器11a至lie與支線9b-9f，用來控制9b-9f支線的開與 關的10b至10k〈開/關〉器，在支線9b - 9f的中間被提供。&lt; 開/關〉器l〇a，用來控制開與關的支線9a在支線9a的中間 被提供。此外，流入N2氣體為了清除在支線内9b-9e中的 殘餘氣體，介於供應源氮氣N2管線9f，以及殘餘的9b至9 e之間的支線之控制開與關器的1 〇 1，1 Op和1 On被提供。氮 氣^除了清除支線9b至9e之外，也清除支線9a以及反應室 1中的殘餘氣體。 如前面所提到的薄膜形成設備1 01，至少含有Si-H鍵2060-4201 -PF; ni vek.ptd V. Description of the invention (9)-Supply source of bonded% oxysilazane (Si 10xane), from, 〇〇, Μ ％, C〇2 'CO' The film-forming gas formed by any selected oxygen-containing gas in the H20 group, the source of H2 supply, and the source of% supply. If Hs has an Aikoxyl compound with Si Η bond, or a film-forming gas of siloxane containing ^ 咄 bond, which is used in the present invention, it will be treated as Typical example to use. (O 3 Aikoxyl compound with Si-fluorene bond) Trimethoxysilane (TMS: SiH (0CH3) 3)) (ii) Si-H bond epoxysilazane (si loxane) Tetramethylsiloxane; TMDS0: (CH3) 2his-0-SiH (CH3) 2) These gases pass through branch lines 9b-9f and branch line 9a in the reaction chamber 1 of the film forming gas supply region 101A The connected places are properly supplied. Flow rate adjusters 11a to lie and branch lines 9b-9f, 10b to 10k <on / off> devices for controlling the opening and closing of the 9b-9f branch line, on the branch lines 9b-9f The middle is provided. &Lt; On / off device 10a, a branch line 9a for controlling opening and closing is provided in the middle of the branch line 9a. In addition, N2 gas is flowed in to remove residual gas in the branch lines 9b-9e, Between the supply source nitrogen N2 line 9f and the remaining 9b to 9e branch control opening and closing switches 10, 1 Op and 1 On are provided. Nitrogen ^ In addition to removing branch lines 9b to 9e, The branch line 9a and the residual gas in the reaction chamber 1 are also removed. As mentioned above, the thin film forming apparatus 101 contains at least Si-H bonds

2060-4201-PF;nivek.ptd 第14頁 5035142060-4201-PF; nivek.ptd p. 14 503514

口 如第2A所示，以及被準備，具有氧化矽薄膜42a的樣 wSi (表示為含矽絕緣薄膜，並且稱為pE-CVD Si % 薄膜，在下文），是以使用含三甲氧基矽烷 2 (Trimethoxysi iane) TMS之薄膜形成氣體的pE —CVD法在矽 基底41上所形成的。為了比較的理由，具有氧化石夕薄膜 51 a的比較樣品c s 1 (表示為含石夕絕緣薄膜，並且稱為 PE - CVD TEOS Si〇2薄膜，在下文），是以使用含四甲氧基 矽烷（tetraethoxysilane) (TE0S)之薄膜形成氣體的 PE-CVD法在矽基底41上所形成的，以及具有氧化矽薄膜 5 2 a的比較樣品c S 2 (表示為含石夕絕緣薄膜，並且稱為 PE-CVD SiH4 Si〇2薄膜，在下文），是以使用含單矽烧 (Monos i lane) (Si Μ之薄膜形成氣體的pe-CVD法在矽基底 41上所形成的。 如第2E圖所示，樣品S1A的形成，是進一步地在As shown in Section 2A, and a sample of wSi (shown as a silicon-containing insulating film and referred to as a pE-CVD Si% film, hereinafter) having a silicon oxide film 42a is prepared using a trimethoxysilane-containing 2 (Trimethoxysi iane) is formed on a silicon substrate 41 by a pE-CVD method of a thin film forming gas of TMS. For comparison reasons, a comparative sample cs 1 (shown as a stone-containing insulating film and referred to as a PE-CVD TEOS SiO 2 film, hereinafter) with a stone oxide film 51 a is used in the presence of a tetramethoxy group A comparative sample cS 2 (expressed as a silicon-containing insulating film) formed by a PE-CVD method of a thin film of tetraethoxysilane (TE0S) on a silicon substrate 41 and a silicon oxide film 5 2 a It is a PE-CVD SiH4 Si02 thin film, which is described below), and is formed on a silicon substrate 41 by a pe-CVD method using a film formation gas containing Monos i lane (Si M). As shown in Section 2E As shown in the figure, the formation of sample S1A is further

PE-CVD TMS Si02薄膜42a上形成一電極板45，在PE-CVD TMS Si〇2薄膜42a上的樣品S1是在矽基底41上所形成的。 水銀彳木針被用來當作電極板4 5 ’以及·-介於水銀探針和 PE-CVD TMS Si02 薄膜42a 的接觸面積為〇.〇23 0cm2。 如第2B圖所示，樣品S2，S3的形成是藉由，形成具有 含有7 mol%磷酸（Phosphorus)和大約50Onm薄膜厚度的 BPSG薄膜43，以及PE-CVD TMS Si〇2 42b薄膜在矽基底41 上所形成。 樣品S2中PE - CVD TMS Si〇2 4 2b薄膜的薄膜厚度被設An electrode plate 45 is formed on the PE-CVD TMS SiO2 film 42a, and a sample S1 on the PE-CVD TMS SiO2 film 42a is formed on a silicon substrate 41. The mercury alder needle was used as the electrode plate 4 5 ′ and the contact area between the mercury probe and the PE-CVD TMS Si02 film 42 a was 0.02 0 cm 2. As shown in FIG. 2B, the samples S2 and S3 were formed by forming a BPSG film 43 containing 7 mol% phosphoric acid (Phosphorus) and a film thickness of about 50 nm, and a PE-CVD TMS SiO 2 42b film on a silicon substrate. 41 on the formation. The film thickness of the PE-CVD TMS SiO 2 4 2b film in sample S2 was set

2060-4201-PF;nivek.ptd 第16頁 503514 五、發明說明（13)2060-4201-PF; nivek.ptd page 16 503514 V. Description of the invention (13)

Signal Co· Ltd所製造），SiLK(商品名），R7(商品名：由 Dow Chemical Co· Ltd所製造）等等，將它塗層上的絕緣 薄膜。具有兩個碳或多於兩個礙的化合物被，特別地，當 做化合物成份，包括在塗層液内。 在第2D圖中所示，樣品S6是籍形成具有150 nm薄膜厚 度的PE-CVD TMS Si02薄膜42d(下保護層），具有2〇〇 nm薄 膜厚度的塗層絕緣薄膜（主要絕緣薄膜）44C，和具有200 nm薄膜厚度的PE-CVD TMS Si02薄膜42e(上保護層），依序 地，在矽基底41上而形成的。塗層絕緣薄膜4 4 C的形成， 是以旋轉塗層（Spin-Coating)塗層液（Fox (商品名））；藉 分解HSQ(Hydrogen silsesquioxane)成為溶劑，然後在氮 氣中分別以150度，200度，與35 0度溫度下烘烤塗層液一 分鐘。為了做比較’比較樣品C S 8使用取代p E - C V D T M S Si〇2薄膜42d的PE-CVD TEOS Si〇2薄膜51d被形成來，當做 下保護層，而且比較樣品CS9使用取代PE-CVD TMS Si02薄 膜42d，42e 的 PE-CVD TEOS Si02 薄膜51d，51e 被形成，2 當 做上及下保護層，被準備起來。 田 | 樣品S1至S6的42a至42e PE-CVD TMS Si02薄膜，在使 用前面所提到的電漿CVD裝置，是以接下來的薄膜形成條 件所形成的。 ' - 薄膜形成氣體：TMS + N20 TMS氣體流率：1〇〇 seem N20氣體流率：30 00 seem 氣壓：0.7 Torr(Manufactured by Signal Co. Ltd.), SiLK (trade name), R7 (trade name: manufactured by Dow Chemical Co. Ltd.), etc., and coated with an insulating film. Compounds having two carbons or more than two barriers are included, in particular, as a component of the compound and are included in the coating liquid. As shown in Figure 2D, sample S6 is a PE-CVD TMS Si02 film with a film thickness of 150 nm (lower protective layer), and a coated insulating film (main insulating film) with a film thickness of 2000 nm. A PE-CVD TMS Si02 film 42e (upper protective layer) having a film thickness of 200 nm was sequentially formed on a silicon substrate 41. The coating insulation film 4 4 C is formed by a spin-coating coating solution (Fox (trade name)); by decomposing HSQ (Hydrogen silsesquioxane) into a solvent, and then at 150 degrees in nitrogen, Bake the coating solution at 200 ° C and 350 ° C for one minute. For comparison, comparative sample CS 8 was formed using PE-CVD TEOS Si02 film 51d instead of p E-CVDTMS Si〇2 film 42d as the lower protective layer, and comparative sample CS9 was used instead of PE-CVD TMS Si02 film PE-CVD TEOS Si02 films 51d, 51e of 42d and 42e are formed, and 2 are prepared as upper and lower protective layers. Tian | The 42a to 42e PE-CVD TMS Si02 films of samples S1 to S6 were formed using the aforementioned plasma CVD apparatus under the following film formation conditions. '-Film-forming gas: TMS + N20 TMS gas flow rate: 100 seem N20 gas flow rate: 30 00 seem Air pressure: 0.7 Torr

2060-4201-PF;n i vek.ptd 第18頁2060-4201-PF; n i vek.ptd p. 18

μ λΛ且，薄膜厚度（1：)是500 nm ,PE-CVD TMS Si02 薄膜 斤射率是3·9。樣品ΠΑ當做樣品被用來檢測相對介 在樣品S1A，相對介電常數是建立在將一具有1〇2頻 罕的小訊號，放置在介於矽基底41和電極板45的DC電壓 v上所獲得的結果，並測量隨著D c電壓（v)的變化而改 的電容所計算出來的。 (i i )碳與氮在薄膜的濃度 碳與氮在PE-CVD TMS Si02薄膜42a的濃度，是以使用 樣品S1的Auger電子光譜法（AES Method)所測量的。 如量測結果，碳的濃度是！·〇 at〇ms% ,而氮的濃度是 2.1 atoms% 〇 (i i i )薄膜密度 碳與氮在PE-CVD TMS Si02薄膜42a的密度使用樣品 S1 以廣知的X-Ray 干涉裝置（X-Ray Interference Methos)或重篁篁測裝置（Weight Measuring method)，所 檢測出來的。 為了要做比較，類似的檢測方式在，熱S i 〇2薄膜， PE-CVD TEOS Si02薄膜51a的比較樣品CS1，與取代PE-CVD TMS Si〇2薄膜42a的比較樣品CS2的PE-CVD SiH4 Si02薄膜 52a 〇 在第3A，3B圖中所示，可發現到PE_CVD TMS Si02薄 膜4 2a有2· 33比其他的絕緣薄膜高的薄膜密度，並且厚。 (iv)薄膜的水氣量μ λΛ, the film thickness (1 :) is 500 nm, and the PE-CVD TMS Si02 film has an emissivity of 3.9. Sample ΠΑ is used as a sample to detect the relative dielectric sample S1A. The relative dielectric constant is obtained by placing a small signal with a frequency of 102 on the DC voltage v between the silicon substrate 41 and the electrode plate 45. The result is calculated by measuring the capacitance that changes with the change in D c voltage (v). (i i) Concentration of carbon and nitrogen in the film The concentration of carbon and nitrogen in the PE-CVD TMS Si02 film 42a was measured using the Auger electron spectroscopy (AES Method) of sample S1. As measured, the carbon concentration is! 〇at〇ms%, and the nitrogen concentration is 2.1 atoms% 〇 (iii) Film density The density of carbon and nitrogen in PE-CVD TMS Si02 film 42a uses sample S1 with the well-known X-Ray interference device (X-Ray Interference Methos) or Weight Measuring method. For comparison, a similar test method is PE-CVD SiH4, a comparative sample CS1 of a thermal Si 02 film, a PE-CVD TEOS Si02 film 51a, and a comparative sample CS2 that replaces the PE-CVD TMS Si02 film 42a. The Si02 thin film 52a is shown in FIGS. 3A and 3B. It can be found that the PE_CVD TMS Si02 thin film 4 2a has a higher film density of 2.33 than other insulating films and is thicker. (iv) Moisture of the film

2060-4201-PF;nivek.ptd 第20頁 503514 發明說明（16) 薄膜的水氣量，使用樣品S1，以TDS( Thermal2060-4201-PF; nivek.ptd Page 20 503514 Description of the invention (16) Moisture of film, using sample S1, TDS (Thermal

Desorption Mass Spectroscopy)法之下，在薄膜形成（層 積）後立刻取得的’以及薄膜在大氣壓中停留兩個星期後 所量測的。 這個TDS法是以，將樣品加熱，然後量測從樣品射出 的分子。為了要做比較的理由，類似的檢測方式在PE — Cvd TEOS Si〇2薄膜51a的比較樣品CS1中被執行。 此檢驗是以TDS分析設備將樣品從室溫加熱到8〇 〇度， 然後量取從樣品蒸餾出的水氣所執行的。 第4圖所示為檢測結果的圖形。第4圖中，一座標圖以 線性比例指出含水氣量（wt%)和一橫座標圖以線性比例指 出溫度（t)。 如薄膜形成（層積）後立刻執行的量測，當溫度從室溫 上升到800度時，PE-CVD TMS Si02薄膜42a的含水氣量是 〇· 1 1 wt%，反之PE-CVD TEOS Si02薄膜51a的含水氣量是 0· 4 9 wt%。此外，如兩個星期後所執行的量測，pE-cvD TMS Si02薄膜42a的含水氣量僅僅增加〇· 2-〇· 3 wt%，因而 含水氣量很少被改變。 如上所述，可發現到’結構水份（g t r u c ^ u r a 1 w a t e r) (薄膜中獲得的水氣量，薄膜形成氣體以及在薄膜形成後 &lt;刻取得的薄膜結構）和物理吸附水份（physical abosorption water)(是被吸附和物理吸附所進入的水 氣），在ΡΕ-CVD TMS Si02薄膜42a中，相反地，比PE-CVD T E 0 S S i 02薄膜5 1 a中來的小。Desorption Mass Spectroscopy) was measured immediately after the film was formed (laminated) and after the film was left in the atmosphere for two weeks. The TDS method involves heating a sample and measuring the molecules emitted from the sample. For comparison reasons, a similar detection method was performed in a comparison sample CS1 of PE-Cvd TEOS SiO2 film 51a. This test is performed by heating the sample from room temperature to 800 ° C with a TDS analysis device, and then measuring the water vapor distilled from the sample. Figure 4 shows a graph of the test results. In Figure 4, a graph indicates the moisture content (wt%) in a linear scale and a horizontal graph indicates the temperature (t) in a linear scale. If the measurement is performed immediately after the film is formed (laminated), when the temperature rises from room temperature to 800 degrees, the moisture content of PE-CVD TMS Si02 film 42a is 0.1 1 wt%, otherwise PE-CVD TEOS Si02 film The water content of 51a is 0.49 wt%. In addition, as a measurement performed two weeks later, the moisture content of the pE-cvD TMS Si02 film 42a only increased by 0.2 to 0.3 wt%, so the moisture content was rarely changed. As mentioned above, 'gtruc ^ ura 1 water' (the amount of water vapor obtained in the film, the film-forming gas, and the film structure obtained after the film formation) and the physical abosorption can be found water) (is the water gas that is absorbed by physical adsorption and physical adsorption). In the PE-CVD TMS Si02 film 42a, on the contrary, it is smaller than that in the PE-CVD TE 0 SS i 02 film 5 1 a.

2060-4201-PF;nivek.ptd 第21頁 5035142060-4201-PF; nivek.ptd p. 21 503514

五、發明說明（17) (v ) FT-IRV. Description of the invention (17) (v) FT-IR

吸附強度 然後，在樣品S1中，以F T - IR分析法（F 〇 u r i e r Transform Infrared analysis method)，的紅外線吸附 強度所檢測的結果在第5 A圖所示。類似地，在比較樣品 CS1，CS2在第5B圖所示。 第5 A圖座標圖中，指出吸附強度是以線性比例被表g (任意單位），而一橫座標圖，指出波數，是以線性比例 (cnr1)所表達，類似地，在第5B圖是真的。 如第5A圖所示，具有中央波數2 270-2350 cm—1的範圍 的紅外線吸附強度的峰值被確認。相反的，如第5 B圖所 示，這樣的峰值並未在樣品CS1，CS2被看到。 (v i )抗水力 第28圖中所示，？£-(^01183102薄膜423的抗水 性’以兩壓潮渔力測試（p r e s s u r e — c 〇 〇 k e r t e s t )在樣品 SI，S2上為例。為了做比較，類似地檢測在使用取代 PE-CVD TMS Si02 薄膜42b 的PE-CVD SiH4 Si02 薄膜51b 的比 較樣品CS3和比較樣品CS5的PE-CVD SiN薄膜53中被應 用0 高壓使潮濕測試的條件在隨後被給予。停留時間 (Leaving time)被用來當做參數。 溫度：1 2 1 度 氣壓：2 atm 潮渔力·· 100 % Κ·Τ (R〇〇m Temperature) 抗水力的評估’是評估在高壓使潮濕測試後，包含在Adsorption Intensity Then, in the sample S1, the results of detection of the infrared adsorption intensity by the F T-IR analysis method (F ore transform analysis method) are shown in Fig. 5A. Similarly, in the comparison samples CS1, CS2 are shown in Figure 5B. The coordinate graph in Figure 5A indicates that the adsorption intensity is expressed in linear scale as g (arbitrary unit), while a horizontal coordinate chart that indicates the wave number is expressed in linear scale (cnr1). Similarly, in Figure 5B it is true. As shown in Fig. 5A, a peak of the infrared absorption intensity having a central wave number in the range of 2 270-2350 cm-1 was confirmed. In contrast, as shown in Figure 5B, such peaks were not seen in samples CS1, CS2. (v i) Water resistance As shown in Figure 28,? £-(^ 01183102 The water resistance of thin film 423 'is based on two pressure tide fishery tests (pressure — c 〇〇〇kertest) on samples SI, S2 as an example. For comparison, similar tests were performed using a replacement PE-CVD TMS Si02 PE-CVD SiH4 Si02 of film 42b, PE-CVD SiN film 53 of comparative sample CS3 and comparative sample CS5 of film 51b were applied. 0 High pressure was used to allow the humidity test conditions to be given later. Leaving time was used as Parameters: Temperature: 1 2 1 degree Air pressure: 2 atm Tide fishing force · 100% Κ · Τ (R〇〇m Temperature) Evaluation of hydraulic resistance 'is evaluated after the high-pressure humidity test, included in

2060-4201-PF;nivek.ptd 第22頁 503514 五、發明說明（18) 檢驗的絕緣薄膜的P = 0鍵量而被執行的。為了要評估包含 在BPSG薄膜43的P = 0鍵量，p = 0的吸附係數在藉著ft-IR分 析法被測量出來。如果水氣進入B P S G薄膜4 3中’在薄膜中 的P = 0鍵因為和水氣反應而消滅。此例，如果為了覆蓋 BPSG薄膜43的PE-CVD TMS Si02薄膜42b有高的抗水力，這 樣的薄膜水氣不會越過，導致BPSG薄膜43的P = 0鍵永遠不 會被消滅。結論，這是有可能性的，P = 〇吸附係數隨時間 而改變，變的比較小的話，抗水力會變的比較大。 第6圖所示，為一包含磷酸的絕緣薄膜的隨時間改變 量’在高壓使潮溼力測試後被執行的圖形。一座標圖，指 出P = 0吸附係數（任意單位）是以線性比例被表達，而一橫 座標圖，指出停留時間（H (hour ))，是以線性比例（cm-i ) 所表達。如第6圖所示的結果，可發現到，即使在樣品 S 2 ’ S 3被停留1 5 〇小時後，他們的P = 〇吸附係數也很不常從 原始P = 0吸附係數改變，不管PE-CVD TMS Si02薄膜42的大 厚度，像比較樣品CS5的PE-CVD SiN薄膜53，這是， PE-CVD TMS Si〇2 薄膜42b 有，相似地，PE-CVD SiN 薄膜53 的抗水力。 而且，抗水力另外以樣品S3與比較樣品CS3，CS4所檢 測的高壓潮溼力測試被檢測。 高壓使潮溼力測試的條件與上述相同。 結果在第7圖所示，第7圖的座標圖指出的抗水力是以 線性比例被表達，而一橫座標圖，指出停留時間 (H(hour))，是以線性比例（cnri)所表達。2060-4201-PF; nivek.ptd Page 22 503514 V. Description of the invention (18) The inspection of the insulating film was performed with P = 0 bond amount. In order to evaluate the amount of P = 0 bond contained in the BPSG film 43, the adsorption coefficient of p = 0 was measured by ft-IR analysis. If water vapor enters the B P S G thin film 43, the P = 0 bond in the film is eliminated because it reacts with water vapor. In this example, if the PE-CVD TMS Si02 film 42b for covering the BPSG film 43 has high water resistance, such film moisture will not be passed, resulting in that the P = 0 bond of the BPSG film 43 will never be eliminated. In conclusion, this is possible. The adsorption coefficient of P = 0 changes with time. If it becomes smaller, the water resistance will become larger. Fig. 6 is a graph showing the change over time of an insulating film containing phosphoric acid 'after a high-pressure wet force test. A plot indicates that the adsorption coefficient (arbitrary unit) of P = 0 is expressed in a linear scale, while a horizontal plot indicates that the residence time (H (hour)) is expressed in a linear scale (cm-i). As can be seen from the results shown in Figure 6, even after the samples S 2 'S 3 were left for 150 hours, their P = 0 adsorption coefficients rarely changed from the original P = 0 adsorption coefficients, regardless of The large thickness of the PE-CVD TMS Si02 film 42 is like the PE-CVD SiN film 53 of the comparative sample CS5. This is that the PE-CVD TMS Si02 film 42b has, similarly, the water resistance of the PE-CVD SiN film 53. Moreover, the water resistance was additionally tested by the high-pressure wet force test detected by the sample S3 and the comparison samples CS3, CS4. The high pressure makes the conditions for the wet force test the same as above. The results are shown in Figure 7, where the water resistance indicated by the coordinate graph of Figure 7 is expressed in a linear scale, and a horizontal graph showing the residence time (H (hour)) is expressed in linear scale (cnri) .

2060-4201-PF;nivek.ptd 第23頁 五、發明說明（19) _ ，品S3，比較樣品CS3，CS4被用來當做參數。 同上’抗水力的評估，是評估在高壓 =檢驗的絕緣薄膜的卜。鍵量而被執行的1 試後， 為基礎所得到的㈣吸附係數，假設為⑽，的”J附係數 測試後計算推知所得到的。 在间壓潮濕力 如第7圖所示，可發現到，樣品S3有 97.4%(100H)，這超過了比較樣品cs3，cs4。力為 (v i i )薄膜的漏電流 被檢測的樣品S1A在第2E圖示 ?月在樣品S卜電極板45,在有薄膜厚度⑴2:'’二本 PE_CVD TMS Si02薄膜42上被形成。 、 流過矽基底41的漏電流和電極板45在加入一介於 底41和電極板45的電壓所測量出來的。 、土 如結果，PE-CVD TMS Si%薄膜42a的漏電流，以電場 強度5 MV/cm的單物質在1〇-8 A/cm2的規則上，且擊穿$壓 (Breakdown Voltage)表示電場是1〇5 MV/cm。 • ★在此情況下，因為本發明的絕緣薄膜本身具有著像 ?N薄膜’很重要地，的小漏電&amp;，不像含矽和碳的絕緣 2膜，為了降低漏電流而弓丨入的氧氣是不需要的。結論， 攻疋=可能地’銅薄膜的表面會被引入的氧氣或引入製程 的氧氣所氧化’而導致來與鋼薄膜接觸的阻隔絕緣薄膜隨 時會剝落。 (Viii )薄膜的黏附力（Adhesiveness)2060-4201-PF; nivek.ptd page 23 5. Description of the invention (19) _, product S3, comparative sample CS3, CS4 are used as parameters. Ibid. The evaluation of water resistance is to evaluate the insulation film under high voltage = inspection. After performing a test with a bond amount, based on the obtained plutonium adsorption coefficient, it is assumed to be plutonium, and it is obtained by calculation and inference after the test of the J-coefficient. The wet force at the intermediate pressure is shown in Fig. 7 and can be found. So far, sample S3 has 97.4% (100H), which exceeds the comparative samples cs3 and cs4. The sample S1A with the force (vii) of the thin film leakage current is shown in Figure 2E. In the sample Sb electrode plate 45, There is a film thickness ⑴2: `` Two PE_CVD TMS Si02 films 42 are formed. The leakage current flowing through the silicon substrate 41 and the electrode plate 45 are measured by adding a voltage between the bottom 41 and the electrode plate 45. As a result, the leakage current of the PE-CVD TMS Si% film 42a is based on the rule of a single substance with an electric field strength of 5 MV / cm on the rule of 10-8 A / cm2, and the breakdown voltage indicates that the electric field is 1. 〇5 MV / cm. • ★ In this case, because the insulating film of the present invention itself has a small leakage current like "N film", it is not like an insulating 2 film containing silicon and carbon. Leakage currents and oxygen inflow are not needed. In conclusion, attack = possibly 'the surface of the copper film will be attracted The barrier film that comes into contact with the steel film is oxidized by the oxygen introduced or the oxygen introduced into the process, and the film will peel off at any time. (Viii) Adhesiveness of the film

503514 五、發明說明（20) 介於如本發明PE-CVD TMS Si02薄膜42c和下置低介電 常數絕緣薄膜44a，44b的黏附力在使用樣品S4，S5而被檢 測。而且’一樣品被控制在薄膜形成前的表面處理和一樣 品沒有被控制在表面處理被準備了，然後，類似的檢測被 執行。在薄膜形成前被執行的表面處理，是用，NHS， Η!等的電漿來將已經做好的表面做重整。 〉 3 在比較方面，PE-CVD TEOS Si02薄膜51c被用來取代 PE-CVD TMS $i〇2薄膜4 2c，且類似的檢驗方式在用無機塗 層絕緣薄膜44a(比較樣品CS6)和有機塗層絕緣薄膜44b(比 較樣品CS7)，當做低介電常數絕緣薄膜，被執行。 在檢驗薄膜的黏附力的測試，剝落測試以利用膠帶 (Tape)和用化學機械研磨CMp(Chemical心叻⑽卜“503514 V. Description of the invention (20) The adhesive force between the PE-CVD TMS Si02 film 42c and the underlying low dielectric constant insulating films 44a and 44b according to the present invention is tested using samples S4 and S5. Moreover, a sample is prepared for surface treatment before film formation and the same product is prepared without being controlled for surface treatment, and then a similar inspection is performed. The surface treatment performed before the film formation is to use a plasma such as NHS, Η !, etc. to reform the prepared surface. 〉 3 In comparison, PE-CVD TEOS Si02 film 51c is used instead of PE-CVD TMS $ i〇2 film 4 2c, and a similar inspection method is used with inorganic coating insulating film 44a (comparative sample CS6) and organic coating The layer insulating film 44b (Comparative Sample CS7) is implemented as a low dielectric constant insulating film. In the test to check the adhesion of the film, the peel test uses a tape and a chemical mechanical polishing CMP (Chemical Xin Lai Bu "

Polishing)的剝落測試，在整個晶圓表面上被執行。 如檢驗結果’不管有沒有薄膜形成前的表面處理， PE-CVD TMS Si〇2薄膜42c對無機塗絕緣薄膜44&amp;和有機塗 絕緣薄膜44b均具有良好的黏附力。相反的，#程度黏附 力的PE-CVD TEOS Si〇2 薄膜51C 比整個pe —CVD IMS SiO 簿 膜42c的黏附力差。然冑，黏附力的差異性是跟著表面2處The peeling test is performed on the entire wafer surface. For example, regardless of whether or not the surface treatment is performed before the film formation, the PE-CVD TMS SiO2 film 42c has good adhesion to the inorganic-coated insulating film 44 &amp; and the organic-coated insulating film 44b. In contrast, the PE-CVD TEOS SiO2 film 51C with a degree of adhesion is worse than the entire pe-CVD IMS SiO film 42c. However, the difference in adhesion is two places following the surface

ΐΐίΐ形ΐ前是否被應用。這是’樣品被控制在薄膜巧 ，二的表面處理’有著比樣品沒有被控制在表面處 兩的黏附力。 C【X)如熱循環（Heat cycle)的缺陷產生率 關=樣品S6和比較樣品CS8，CS9，如熱循環（Heat cycle)的缺陷產生率被檢測。對照的樣品被封在封裝是否 ίΐ 形 ΐ Was applied before. This is that 'the sample is controlled on the film, and the surface treatment of the two' has a higher adhesion than the sample is not controlled on the surface. C [X] Defect generation rate such as heat cycle Off = Sample S6 and comparative samples CS8, CS9, defect generation rate such as heat cycle are detected. The control sample is sealed in a package

503514503514

(Package)中。熱循環的測試條件在接下來被給予。循環 數被使用為參數。 高溫（持續時間）：150度（2〇 minutes ) 低=(持續時間）：—55度（2〇 minutes )(Package). Test conditions for thermal cycling are given next. The number of cycles is used as a parameter. High temperature (duration): 150 degrees (20 minutes) Low = (duration): -55 degrees (20 minutes)

循環數：1〇〇，200，300，500 C 窃結果在第9圖示出。第9圖的座標圖指出的缺陷產生率 U)是以線性比例被表達，而一橫座標圖，指出樣品的種 類。樣品的種類為，樣品S6和比較樣品CS8，CS9，在前面 解釋過’依序地，從左邊。@開的面積是指示出，在特定 循環數時，出缺陷數（Fraction defective)的柱狀圖，隔 =的面積是由指出缺陷數在1〇〇度時的橫向線所畫出的， 隔開的面積是由指出缺陷數在200度時的垂直線所晝出 的’隔開的面積是由指出缺陷數（Fracti〇n defective)在 300度時的斜線所畫出的。在黑底上和白色隔開的面積是 指出缺陷數在5〇〇度。 如第9圖示出，樣品6在使用當做上保護層與下保護層 的f發明的氧化矽，缺陷在300度或更高時被產生出來， 仁疋缺fo、產生率是約2 — 3 %，即使缺陷產生率在goo度或 500度^夺增加。比較樣品CS8，在使用本發明的氧化矽52d f，當做在上保護層與下保護層的下保護層，缺陷機乎在 ，0度到5 〇 〇度時被很一致地產生出來，且整個缺陷產生 率約25 %。比較樣品以9，在不使用上保護層與下保護層 的本發明的氧化矽42d，42e時，缺陷機乎從1〇0度到5〇〇度 時被產生出來’特別說明的是，缺陷產生率在300度或500Number of cycles: 100, 200, 300, 500 C The theft results are shown in Figure 9. The graph in Figure 9 indicates the defect occurrence rate U) is expressed in a linear scale, while a horizontal graph indicates the type of sample. The types of the samples are sample S6 and comparative samples CS8 and CS9, which were explained earlier 'in order, from the left. The area of @ 开 is a histogram indicating the number of defects (Fraction defective) at a certain number of cycles. The area of the interval = is drawn by a horizontal line indicating the number of defects at 100 degrees. The open area is drawn by a vertical line indicating the number of defects at 200 degrees, and the separated area is drawn by the oblique line indicating the number of defects (Fraction defect) at 300 degrees. The area separated from white on the black background indicates that the number of defects is 500 degrees. As shown in Fig. 9, the sample 6 uses the silicon oxide invented by f as the upper protective layer and the lower protective layer. Defects are generated at 300 degrees or higher. The defect rate is about 2-3. %, Even if the defect generation rate increases at 500 degrees or 500 degrees. Comparative sample CS8, when using the silicon oxide 52d f of the present invention, as the lower protective layer on the upper protective layer and the lower protective layer, the defect mechanism is almost uniformly generated from 0 degrees to 5000 degrees, and the entire The defect generation rate is about 25%. The comparison sample is 9, when the silicon oxide 42d, 42e of the present invention without the upper protective layer and the lower protective layer is used, the defect mechanism is generated from 100 degrees to 500 degrees. 'Specifically, the defect Production rate at 300 degrees or 500

503514 五、發明說明（22) 度時增加，且整個缺陷產生率約53 %。 (X )對銅薄膜的阻隔特性檢測 (a)TDDB(Time Dependent Dielectric Breakdown )測試 TDDB測試是，當電壓被用在樣品時，到達介電擊穿 (Dielectric Breakdown)所需要的時間 〇 此被檢測的樣品的準備是被依序地層疊，如本發明的 PE-CVD TMS Si〇2薄膜和在石夕基底上的銅薄膜。在比較方 面，類似的檢測被應用來使用取代PE-CVD TMS Si02薄膜 的PE-CVD TEOS Si〇2薄膜的樣品，且此樣品置入TiN薄膜 介於銅薄膜和PE-CVD TEOS Si02薄膜之間。 如檢驗結果，10 X 1〇5秒的擊穿壽命（breakd〇wn lifetime)是在電場強度為8 MV/cm時所取得的。 相反的，在使用PE-CVD TEOS Si02薄膜的樣品，在電 場強度為8 ΜV/cm時，可得到每1 〇 x 1 〇5秒規則的擊穿壽 命。這意味著，使用ΡΕ-CVD TMS S i 02薄膜樣品的擊穿壽 命比使用PE-CVD TEOS Si02薄膜的樣品多了機乎六位數。 在置入TiN薄膜介於銅薄膜和PE_CVD te〇S Si02薄膜 之間的樣品’在電場強度為7· 5 MV/cm時，可得到每1 〇 x 1 05秒規則的擊穿壽命。 和上面，這是可以認為，使用PE-CVD TMS Si〇2薄膜 樣品的擊穿壽命比使用PE-CVD TE〇s Si〇2薄膜的樣品多了 機乎六位數，且對銅有阻隔特性，這是和TiN薄膜相似 的，或著比它還多。503514 Fifth, the description of the invention increases at (22) degrees, and the entire defect generation rate is about 53%. (X) Detection of the barrier properties of copper films (a) TDDB (Time Dependent Dielectric Breakdown) test The TDDB test is the time required to reach the Dielectric Breakdown when the voltage is applied to the sample. This is detected The preparation of the samples is sequentially laminated, such as the PE-CVD TMS SiO 2 film of the present invention and the copper film on a Shi Xi substrate. In comparison, a similar test was applied to use a sample of PE-CVD TEOS Si02 film instead of PE-CVD TMS Si02 film, and this sample was placed between a TiN film between a copper film and a PE-CVD TEOS Si02 film . As a result of the test, a breakdown lifetime of 10 × 105 seconds was obtained at an electric field strength of 8 MV / cm. In contrast, when using a PE-CVD TEOS SiO2 thin film, the electric field strength was 8 MV / cm, and a regular breakdown life per 10 x 105 seconds was obtained. This means that the breakdown life of the PE-CVD TMS Si 02 thin film sample is almost six digits longer than that of the PE-CVD TEOS Si02 thin film sample. When a sample of a TiN thin film interposed between a copper thin film and a PE_CVD te0S Si02 thin film is placed, when the electric field strength is 7.5 MV / cm, a regular breakdown life per 10 x 105 seconds can be obtained. As above, it can be considered that the breakdown life of the samples using PE-CVD TMS Si〇2 film is more than six digits longer than that of samples using PE-CVD TE〇s Si〇2 film, and it has barrier properties to copper This is similar to or more than TiN film.

503514 五、發明說明（23) (b)熱阻抗的檢測（jjeat Resistance) 如第1 0圖示出，此被檢測的樣品的準備是層疊，如本 發明的125mn厚度的PE —CVD TMS Si02薄膜與在矽基底上的 銅薄膜（未顯示），因而互相接觸在一起。 此檢測是量測PE-CVD TMS Si02薄膜中的濃度分佈狀 態，在以薄膜形成（以第1 〇圖的點線所代表）後立刻取得的 狀態的基礎上，在樣品已做了預設的時間後（三種，即 是，1小時（連鎖雙破折線），7小時（實線），15小時（點一破 折線）），在470度的溫度下。 第1 0圖所示為檢測結果的圖形。第1 〇圖，在左邊的座 標圖指出銅濃度，與矽濃度（cm-3 )，被表達為對數比例 (Logarithmic scale)。橫座標圖，指出量測從pE一cvd TMS Si〇2薄膜表面到銅薄膜邊的深度（nm)是線性比例 (Linear Scale) ° 如第1 0圖所示，分佈是不常從薄膜形成後立刻取得的 分佈而改變。換句話說’可發現到，TMS Si02薄 膜對銅有著非常有效的阻隔特性。503514 V. Description of the invention (23) (b) Detection of thermal resistance (jjeat Resistance) As shown in Fig. 10, the preparation of the tested sample is laminated, such as the PE-CVD TMS Si02 film with a thickness of 125mn according to the present invention. And a copper film (not shown) on a silicon substrate, and thus contact each other. This test is to measure the concentration distribution state in the PE-CVD TMS Si02 film. Based on the state obtained immediately after the film formation (represented by the dotted line in Figure 10), the sample has been preset. After time (three kinds, that is, 1 hour (chain double dashed line), 7 hours (solid line), 15 hours (pointed dash line)), at a temperature of 470 degrees. Figure 10 shows the graph of the test results. In Fig. 10, the graph on the left indicates that the copper concentration and the silicon concentration (cm-3) are expressed as a logarithmic scale. The horizontal coordinate graph indicates that the depth (nm) measured from the surface of the pE-cvd TMS Si02 film to the edge of the copper film is a linear scale. As shown in Figure 10, the distribution is not very common after film formation. The distribution obtained immediately changes. In other words, it can be found that the TMS Si02 film has very effective barrier properties to copper.

在上述，含有Si-H鍵之烷氧基化合物（Alk〇xyl compound)，如TMS，被使用，當做含矽氣體在薄膜形成氣 體中。但是，含有Si-H鍵之環氧矽氮烷（su〇xane)也可能 被使用。 而且，在上述，Νζ0被用來當做含氧氣體。但是，從 〇2 ’ N〇2 ’ C〇2 ’ C0，及群組中任何一個所選出的也可能 被使用。In the above, an Alxoxyl compound containing a Si-H bond, such as TMS, is used as a silicon-containing gas in a film-forming gas. However, epoxy-containing siloxanes (suoxane) containing Si-H bonds may also be used. Furthermore, in the above, Nζ0 is used as an oxygen-containing gas. However, those selected from 〇2 'No2' Co2'C0, and any one of the groups may also be used.

503514 五、發明說明（24) &quot;~——^ 此外，如果從％與札群組中任何一個所選出而被加 上述的薄膜形成氣體，則密度可以更增加。 (第三實施例） θ 接下來，如本發明的第三實施例的半導體裝置以 裝置製造方法將在下文參考第11Α與11Β圖而被解釋。、 如第11Β圖所示，根據本發明的氧化矽24 (含矽絕 薄膜）在基底20a上形成。基底2〇中，下置絕緣薄膜22 及導電佈線23在主基底21上形成。氧化矽薄膜24覆蓋 電佈線2 3。根據本發明的氧化石夕薄膜2 &amp;，具有波數 2270-2350 cnr1範圍的紅外線吸附強度的峰值，以及 2. 25-2· 40 g/cm3範圍的薄膜密度，以及3· 3 —4· 3範圍 對介電常數。 在追個情況下，藉著形成導電佈線以及絕緣薄膜，在 可被用來當作Base基底21的矽基底上，可得到石夕基底或503514 V. Description of the invention (24) &quot; ~ —— ^ In addition, if the above-mentioned film-forming gas is selected from any of the% and Zha groups, the density can be further increased. (Third Embodiment) θ Next, a semiconductor device according to a third embodiment of the present invention will be explained with reference to FIGS. 11A and 11B by a device manufacturing method. As shown in FIG. 11B, a silicon oxide 24 (silicon-containing insulating film) according to the present invention is formed on a substrate 20a. In the substrate 20, a lower insulating film 22 and a conductive wiring 23 are formed on the main substrate 21. The silicon oxide film 24 covers the electrical wiring 2 3. According to the present invention, the oxidized stone film 2 &amp; has a peak of infrared absorption intensity in a range of 2270-2350 cnr1, and a film density in a range of 2.25-2 · 40 g / cm3, and 3. · 3-4. · 3 ranges versus dielectric constant. In this case, by forming a conductive wiring and an insulating film, on a silicon substrate that can be used as the Base substrate 21, a Shi Xi substrate or

Base基底。如鋁（A1)、銅（Cu)等，的傳導材料可被用 當作導電佈線23的材料。 在這個情況下，根據本發明的氧化矽薄膜2 4，可被當 作覆蓋以鋁（A1)、銅（Cu)等，的傳導材料所做之導電佈 線23的絕緣薄膜。 如第三實施例的半導體裝置，如本發明的含矽絕緣薄 膜24是被形成來接觸以及導電佈線23。 上述含矽絕緣薄膜2 4具有一些特性，如、厚、優良的 抗水力、以及類似於SiN薄膜；低水氣在薄膜中，以及比 S1 N薄膜低的介電常數。結論，如果如本發明的含矽絕緣Base. A conductive material such as aluminum (A1), copper (Cu), etc. can be used as the material of the conductive wiring 23. In this case, the silicon oxide film 24 according to the present invention can be used as an insulating film of the conductive wiring 23 made of a conductive material covered with aluminum (A1), copper (Cu), or the like. Like the semiconductor device of the third embodiment, the silicon-containing insulating film 24 of the present invention is formed to contact and conduct the wiring 23. The above-mentioned silicon-containing insulating film 24 has some characteristics, such as, thick, excellent water resistance, and is similar to SiN film; low water vapor in the film, and a lower dielectric constant than S1 N film. In conclusion, if the silicon-containing insulation as in the present invention

503514 五、發明說明（26) 然後，導電佈線（下導電佈線）23在下置絕緣薄膜22 上被形成。然後，如第11B圖所示，約5〇〇 nm薄膜厚度的 PE-CVD TMS Si02 薄膜24，以用來形成pe-CVD TMS Si02 薄 膜22的電漿CVD法來形成。 如上所述，如本發明的第三實施例，下置絕緣薄膜2 2 是在矽基底21上在導電佈線23前被形成的。PE-CVD TMS Si 〇2薄膜疋厚、具優良4几水力、以及低水氣在薄膜中。所 以，下置絕緣薄膜22，可防止在下置絕緣薄膜22中以及外 來的水氣滲透進入矽基底21。503514 V. Description of the invention (26) Then, a conductive wiring (lower conductive wiring) 23 is formed on the lower insulating film 22. Then, as shown in FIG. 11B, a PE-CVD TMS Si02 thin film 24 having a film thickness of about 500 nm is formed by a plasma CVD method for forming a pe-CVD TMS Si02 thin film 22. As described above, as in the third embodiment of the present invention, the lower insulating film 2 2 is formed on the silicon substrate 21 before the conductive wiring 23. The PE-CVD TMS Si 〇2 film is thick, has excellent hydraulic strength, and low moisture in the film. Therefore, the lower insulating film 22 can prevent the moisture in the lower insulating film 22 and the outside from penetrating into the silicon substrate 21.

此外，因為導電佈線23以及矽基底21間的漏電流可被 抑制住，電晶體、記憶體元件之電容、等，被ΡΕ-CVD TMS S i 02薄膜所覆蓋，當他們是在矽基底21上形成的時候。所 以’外流的聚積電荷（accumulated charge)可被防止， 導致裝置的可靠度提升。 此外，因為PE-CVD TMS Si02薄膜24是在導電佈線23 被覆蓋之後形成的，在薄膜24中以及外來的水氣所導致導 電佈線23的腐蝕可被防止。 進一步，因為PE-CVD TMS Si02薄膜24有比SiN薄膜低In addition, because the leakage current between the conductive wiring 23 and the silicon substrate 21 can be suppressed, the capacitance of the transistor, the memory element, etc. are covered by the PE-CVD TMS S i 02 film. When they are on the silicon substrate 21 When formed. Therefore, the 'accumulated charge' outflow can be prevented, leading to an increase in the reliability of the device. In addition, since the PE-CVD TMS SiO 2 film 24 is formed after the conductive wiring 23 is covered, corrosion of the conductive wiring 23 caused by the moisture in the film 24 and from outside can be prevented. Further, because the PE-CVD TMS Si02 film 24 is lower than the SiN film

的相對介電常數以及低漏電流，介於導電佈線2 3間的漏電 流可被抑制以及介於導電佈線2 3間的寄生電容可被減少， 在相鄰之複數導電佈線或多層次導電佈線形成的情況之 下。 (第四實施例） 接下來，如本發明的第四實施例的半導體裝置之製造Relative dielectric constant and low leakage current, the leakage current between conductive wirings 2 and 3 can be suppressed and the parasitic capacitance between conductive wirings 2 and 3 can be reduced. In adjacent multiple conductive wirings or multi-level conductive wirings Formation of the situation. (Fourth Embodiment) Next, a semiconductor device according to a fourth embodiment of the present invention is manufactured.

2060-4201-PF;nivek _ 第31頁 五、發明說明（27) 方H下圖文:/考第l2A與i2c圖而被解釋。 視圖。 θ ’、為如本發明第四實施例的半導體裝置斷面 絕绫ί 312?·圖所示，低介電常數絕緣薄膜25，如多孔隙 絶緣溥膜、S i 〇 ρ蒱_ ^ 9Q , ^ ^ 4膜、或類似，被形成來覆蓋導電佈線 俾1二六明之氧化矽薄膜（含矽絕緣薄膜）所做成的 保濩層26在絕緣薄膜25上被形成。 认ί ^明之保護層26，具有波數2270 — 2350 cm—1範圍的 ^汽、择吸附強度的峰值，以及2·25 — 2·4〇 g/cm3範圍的薄 、猎又，以及3. 3-4· 3範圍的相對介電常數。 # π如ΐ所述之氧化矽薄膜26有類似氮化矽（SiN)薄膜的 ' 。氧化矽薄膜26，有較低的相對介電常數、厚、高抗 ^ 低水軋里在薄膜中。結論，如果如本發明的含矽絕 /膜，被用來當作覆蓋導電佈線23的保護層26、等，導 電佈線23的腐餘可在防止外來水氣滲透的情況之下被防 止，當減少導電佈線23間的寄生電容（parasHic capacitance) 〇 具體說明’如果多孔隙薄膜被用來當做覆蓋導電佈線 23的絕緣薄膜25，則欲進入多孔隙薄膜的外來水氣可被防 止’並且介電常數也會因為水氣吸附的防止而增加。 第1 2 A與1 2 C圖係如本發明第四實施例的半導體裝置斷 面視圖。TMS + Ne被用來當做薄膜形成氣體。 首先，如第12A圖所示，同第三實施例，由PE —CVD TMS Si〇2薄膜所做成的下置絕緣薄膜22，是以TMS + N2〇為薄2060-4201-PF; nivek _ page 31 V. Description of the invention (27) Fang H The following picture: / Explained by examining the l2A and i2c pictures. view. θ ′, as shown in the section 312 of the semiconductor device according to the fourth embodiment of the present invention, a low dielectric constant insulating film 25, such as a multi-porous insulating film, S i 〇ρ 蒱 _ ^ 9Q, ^ ^ 4 film, or the like, is formed on the insulating film 25 to form a protective layer 26 made of a silicon oxide film (including a silicon insulating film) that covers the conductive wiring 126. It is recognized that the protective layer 26 of Ming has a peak of the wave number 2270-2350 cm-1, a peak of selective adsorption intensity, and a thin, hunting range of 2.25-2.40 g / cm3, and 3. Relative dielectric constant in the range of 3-4 · 3. # π The silicon oxide film 26 described above has a silicon nitride (SiN) film-like '. The silicon oxide film 26 has a low relative permittivity, is thick, has a high resistance, and has a low water rolling in the film. In conclusion, if the silicon-containing insulation / film of the present invention is used as a protective layer 26 covering the conductive wiring 23, etc., the residue of the conductive wiring 23 can be prevented under the condition of preventing the penetration of external water vapor. Reduce parasHic capacitance between conductive wirings 23 〇Specify 'if a porous film is used as the insulating film 25 covering the conductive wiring 23, the external water and gas entering the porous film can be prevented' and the dielectric The constant will also increase due to the prevention of moisture adsorption. 12A and 12C are cross-sectional views of a semiconductor device according to a fourth embodiment of the present invention. TMS + Ne is used as a film-forming gas. First, as shown in FIG. 12A, as in the third embodiment, a lower insulating film 22 made of a PE-CVD TMS SiO2 film is made of TMS + N2O as a thin film.

2060-4201-PF;nivek.ptd 第32頁 503514 五、發明說明（29) 五實施例，TMS + N20是用來當做PE-CVD TMS Si〇2薄膜的薄 膜形成氣體。 第1 3F圖係為如本發明第五實施例的半導體裝置斷面 視圖。 如第13F圖所示，半導體裝置中，下置絕緣薄膜32是 在Base基底31上形成的，以及下導電佈線33在下置絕緣薄 膜32隨後形成。進一步，層間絕緣薄膜32被形成來接觸以 及覆蓋下導電佈線33。第11B圖中，同Base基底21的Base 基底被用來當作Base基底31。 層間絕緣薄膜的形成是將，如本發明中由含石夕絕緣薄 膜所形成之下保護層34，主要絕緣薄膜35、如本發明中由 含矽絕緣薄膜所形成之上保護層3 6，依序從下層層疊所形 成的。 如本發明中含矽絕緣薄膜，具有波數227〇-235〇 cf 範圍的紅外線吸附強度的峰值，以及2· 25_2· 4〇 g/cm3範 圍的薄膜德、度’以及3·3-4·3範圍的相對介電常數。 在此例中，多孔隙絕緣薄膜或§iQF薄膜，是具有低介 電常數的絕緣薄膜，可被用來當作絕緣薄膜3 5。 此外，接觸孔37是在層間絕緣層中的下導電佈線33上 所形成的。下導電佈線33以及上導電佈線38是經過接觸孔 37而連接起來。 如上所不，如第五實施例，因為pE-CVD TMS Si%薄 膜所做成的下保護層34是形成來覆蓋下導電佈線33，下保 濩層34中所含有的水氣以及外來水氣所導致導電佈線33的2060-4201-PF; nivek.ptd Page 32 503514 V. Description of the Invention (29) In the fifth embodiment, TMS + N20 is used as a thin film forming gas for PE-CVD TMS SiO 2 thin film. Fig. 13F is a sectional view of a semiconductor device according to a fifth embodiment of the present invention. As shown in Fig. 13F, in the semiconductor device, the lower insulating film 32 is formed on the Base substrate 31, and the lower conductive wiring 33 is formed later on the lower insulating film 32. Further, an interlayer insulating film 32 is formed to contact and cover the lower conductive wiring 33. In FIG. 11B, the Base base 21 which is the same as the Base base 21 is used as the Base base 31. The interlayer insulation film is formed by, for example, a lower protective layer 34, a main insulating film 35, and an upper protective layer 36 formed by a silicon-containing insulating film, as in the present invention. The order is formed by stacking from the lower layer. For example, the silicon-containing insulating film in the present invention has a peak value of infrared absorption intensity in a wavenumber range of 227 ° -235 ° cf, and a film in the range of 2.25_2 · 40g / cm3, degree, and 3.3-4 · Relative dielectric constant in 3 ranges. In this example, a porous insulating film or §iQF film is an insulating film having a low dielectric constant and can be used as the insulating film 35. Further, a contact hole 37 is formed on the lower conductive wiring 33 in the interlayer insulating layer. The lower conductive wiring 33 and the upper conductive wiring 38 are connected through a contact hole 37. As above, as in the fifth embodiment, the lower protective layer 34 made of pE-CVD TMS Si% film is formed to cover the lower conductive wiring 33, the moisture contained in the lower retaining layer 34, and the external moisture. Caused by conductive wiring 33

第34頁 503514Page 503 514

腐蝕可被防止。 ;:及下進;==二 薄膜所形成，則進入上 周邊部份之氟（F )元 如果主要絕緣薄膜35是以Si 〇F 保護層34以及下保護層36中的外部 素的擴散可被防止。 此外，如果由多孔隙絕緣薄膜所形成的主要絕緣薄膜 35被形成，則吸濕能力會提高，且介電常數會隨著水氣吸 附而改k然而，如果主要絕緣薄膜3 5夾層在上保護層3 4 ，及下保護層36之間，則進入主要絕緣薄膜託中之外來水 氣的滲透可以被抑制，並導致層間絕緣薄膜的介電常數， 可以被穩定在低值。此外，包含多孔隙絕緣薄膜的整體層 間絕緣薄膜漏電流可被抑制。Corrosion can be prevented. ;: And downward; == formed by two thin films, then enter the fluorine (F) element in the upper peripheral portion. If the main insulating film 35 is diffused by the outer element in the Si 0F protective layer 34 and the lower protective layer 36, Be prevented. In addition, if the main insulating film 35 formed of the porous insulating film is formed, the moisture absorption capacity will be improved, and the dielectric constant will be changed with the adsorption of water vapor. However, if the main insulating film 35 is sandwiched on top and protected Between the layers 3 4 and the lower protective layer 36, the penetration of external moisture into the main insulating film holder can be suppressed, and the dielectric constant of the interlayer insulating film can be stabilized at a low value. In addition, the entire interlayer insulating film including the porous insulating film can be suppressed from leaking current.

更進一步，PE-CVD TMS Si〇2薄膜34、36，具有比SiN 薄膜小的相對介電常數，以及低漏電流。所以，在緊密排 列複數導電佈線或多層次導電佈線的形成的例子中，介於 導電佈線間的漏電流可被抑制以及介於導電佈線間的寄生 電容也可被減少。 ° 在此例中，如果下置絕緣薄膜是形成在以如本發明中 所形成的PE-CVD TMS Si〇2薄膜上形成的話，則下置絕緣 薄膜32的水氣以及到Base基底31的外來水氣，可被防 止。此外，如果矽基底是用來當作Base基底31，介於下 導電佈線33以及Base基底31間的漏電流。所以，以電晶Furthermore, PE-CVD TMS SiO 2 films 34 and 36 have a relative dielectric constant smaller than that of SiN films and low leakage current. Therefore, in the case of forming a plurality of closely-conducted wirings or multi-layered conductive wirings, the leakage current between the conductive wirings can be suppressed and the parasitic capacitance between the conductive wirings can be reduced. ° In this example, if the underlying insulating film is formed on a PE-CVD TMS SiO 2 film as formed in the present invention, the moisture of the underlying insulating film 32 and the foreign matter to the Base substrate 31 Water vapor can be prevented. In addition, if the silicon substrate is used as the Base substrate 31, the leakage current between the lower conductive wiring 33 and the Base substrate 31. So with the crystal

2060-4201-PF;nivek.ptd 第35頁 503514 五、發明說明（32) 然後’如第1 3圖所示，具有低介電常數以及約5 0 〇 n m 薄膜厚度的多孔隙絕緣薄膜是由廣知的電漿CVD法所形成 的。如形成多孔隙絕緣薄膜的方法，有形成多層次絕緣薄 膜的方法，是藉著低壓電漿CVD法以及電漿CVD法來重複薄 膜开&gt; 成的方法，將有機（organic)薄膜以及薄膜交替 地層疊而成，並然後以氧電漿之灰分法（ashing )將有機 薄膜移除，等，舉例來說。 然後，如第13D圖所示，一薄且高厚度之NSG薄膜（未 被形成 的，當 s有摻雜氧化石夕薄膜），當作保護層（上保護層），以餘 刻以及灰分的多孔隙絕緣薄膜被形成。如果保護層36沒有 ’則多孔隙絕緣薄膜35的品質是由製程氣體來改變 光阻層的灰分被執行時或當多孔隙絕緣薄膜35下的 阻隔絕緣薄膜34被蝕刻時，並導致，低介電常數特徵降低 的可此性。保護層3 6可被忽略在此例中。 、然後’如第1 3E圖所示，光阻層（未顯示）被形成以 及然後’開放部份在光阻層之接觸孔形成區域，以將光阻 層圖案化而形成。然後，首先，光阻層中經過開放部份的 保護層36，使用含有CF4 + CHf3電漿混合氣體之 RIECreactive i〇n etching)被蝕刻以及除去。妙 ，絕緣薄膜35 ’使用含有cF4 + (：HF3之混合氣胃f其組成 比疋從保護層36中所使用的㈣氣體加以改變，被#刻以 去二ί論丄一用來曝露阻隔絕緣薄膜34的開放部份被 二ίί…Γ層的灰分被執行。在這時候，阻隔絕緣 4膜34擁有抵抗㈣多孔隙絕緣薄膜35之钱刻氣體，以及2060-4201-PF; nivek.ptd Page 35 503514 5. Description of the invention (32) Then 'as shown in Figure 13, the porous dielectric film with a low dielectric constant and a film thickness of about 500 nm is composed of It is formed by the well-known plasma CVD method. For example, a method of forming a porous insulating film includes a method of forming a multi-layered insulating film, which is a method of repeating the opening of a thin film by a low-voltage plasma CVD method and a plasma CVD method, and an organic film and a thin film. Laminated alternately, and then organic thin films are removed by ashing with an oxygen plasma, etc., for example. Then, as shown in FIG. 13D, a thin and high-thickness NSG film (unformed, when s is doped with oxide film) is used as a protective layer (upper protective layer). A porous insulating film is formed. If the protective layer 36 is not provided, the quality of the porous insulating film 35 is changed by the process gas when the ash content of the photoresist layer is performed or when the barrier insulating edge film 34 under the porous insulating film 35 is etched and results in low dielectric Reduced electrical constant characteristics. The protective layer 36 can be omitted in this example. Then, as shown in FIG. 13E, a photoresist layer (not shown) is formed, and then an open portion is formed in a contact hole forming area of the photoresist layer to pattern the photoresist layer. Then, first, the protective layer 36 passing through the open portion of the photoresist layer is etched and removed using RIECreactive ion etching (containing CF4 + CHf3 plasma mixed gas). Miao, the insulating film 35 'uses a mixed gas containing cF4 + (: HF3), and its composition ratio is changed from the radon gas used in the protective layer 36, and is engraved by # 刻 以 去 二The open portion of the film 34 is performed by two layers of ash. At this time, the barrier edge 4 film 34 has a gas engraved with the anti-porous insulating film 35, and

503514503514

光阻層之灰分亂體的能力。結論，導電佈線33沒有被餘刻 氣體很嚴重的影響，等。含有eF4+CHF3之混合氣體濃度比 可藉由增加Ar + 02，等來做調整。除了蝕刻氣體之外。 然後，阻隔絕緣薄膜34在保護層36以及多孔隙絕緣薄 膜35中的開放部份，以使用含有CF4 + CHF3電漿混合氣體之 KIECreactive ion etching)被蝕刻以及除去，此有和前 面的保護層36在蝕刻所使用相同的氣體濃度比。結論，從 其底部來曝露阻隔絕緣薄膜34的接觸孔被形成。在這時 候’下導電佈線3 3擁有抵抗蝕刻前面的阻隔絕緣薄膜3 4之 蝕刻氣體的能力。結論，導電佈線33沒有被蝕刻氣體很嚴 重的影響，等。在這時候，導電佈線33的表面被氧化。 但’像這樣的氧化層，以稀釋氫氣電漿，舉例，惰性氣 體，如NHS、氬氣、氮氣、或類似的，在光阻層之灰分以 及阻隔絕緣薄膜之餘刻階段完成以後，可被除去。 然後，如第1 3 F圖所示，傳導薄膜在接觸孔中被填 滿。然後，由銅或鋁所做成之上導電佈線38，在經過傳導 薄膜’與下導電佈線33連結。如果上導電佈線38是銅導電 佈線，包括阻隔金屬薄膜之下置傳導薄膜如TaN，以及以 濺鍍法所形成之銅膜，在接觸孔37中被提供，然後，傳導 薄膜在其上隨後形成。 由上述，上導電佈線38被形成。上導電佈線38，在經 過保護層36、阻隔絕緣薄膜34、以及多孔隙絕緣薄膜35中 之接觸孔，與下導電佈線33連結。 如上所述，如第五實施例，下導電佈線33被本發明所The ability of the photoresist layer to mess with ash. In conclusion, the conductive wiring 33 is not seriously affected by the remaining gas, etc. The concentration ratio of the mixed gas containing eF4 + CHF3 can be adjusted by adding Ar + 02 and so on. Except for etching gas. Then, the open portions of the barrier film 34 in the protective layer 36 and the porous insulating film 35 are etched and removed using KIECreactive ion etching containing a CF4 + CHF3 plasma mixed gas). The same gas concentration ratio is used in the etching. In conclusion, a contact hole exposing the barrier film 34 from its bottom is formed. At this time, the conductive wiring 3 3 has the ability to resist the etching gas of the barrier film 3 4 in front of the etching. In conclusion, the conductive wiring 33 is not severely affected by the etching gas, and so on. At this time, the surface of the conductive wiring 33 is oxidized. But 'oxidized layers like this to dilute the hydrogen plasma, for example, inert gases such as NHS, argon, nitrogen, or similar, can be removed after the completion of the remaining stages of the ash of the photoresist layer and the barrier film Remove. Then, as shown in Fig. 1F, the conductive film is filled in the contact hole. Then, the upper conductive wiring 38 made of copper or aluminum is connected to the lower conductive wiring 33 via a conductive film '. If the upper conductive wiring 38 is a copper conductive wiring, a conductive film including a barrier metal film such as TaN, and a copper film formed by a sputtering method are provided in the contact hole 37, and a conductive film is subsequently formed thereon . From the above, the upper conductive wiring 38 is formed. The upper conductive wiring 38 is connected to the lower conductive wiring 33 through contact holes in the protective layer 36, the barrier film 34, and the porous insulating film 35. As described above, as in the fifth embodiment, the lower conductive wiring 33 is

503514 五、發明說明（34) 所 使用的PE-CVD TMS Si〇2薄膜所做成之阻隔絕緣薄膜 覆蓋。 順便，如第二實施例的檢驗結果所表示的，如 之PE-CVD TMS Si〇2薄膜，有類似氮化矽（siN)薄骐發月 點。PE-CVD TMS Si〇2薄膜，厚、有良好的抗水性、、，優 氣量在薄膜中。結論，下導電佈線33的腐蝕可在防止&amp; 水氣滲透的情況之下被防止。 夕來 此外，如果下置阻隔絕緣薄膜32是由如本發明之 PE-CVD TMS Si〇2薄膜所形成的，則下導電佈線33的所 周邊電路部分可被PE-CVD TMS Si〇2薄膜所保護。所以， 下導電佈線3 3的腐蝕可在防止下導電佈線33的所有 路部分水氣滲透的情況之下被防止。 ” 進一步，具有低介電常數之多孔隙絕緣薄膜35的上 表面，以ΡΕ-CVD TMS Si〇2薄膜所形成的阻隔絕緣薄膜34 以及PE-CVD TMS Si〇2薄膜所形成的保護層36，被保護起 來。結論，進入多孔隙絕緣薄膜35中的外來水氣滲透可被 防止。所以，根據多孔隙絕緣薄膜35中含有的水氣量而變 化的介電常數可被抑制。 更進一步’如果孔隙絕緣薄膜35中含有的水氣是一開 始就有的，流出到周邊電路部分的水氣可被防止，並導 致，下導電佈線33的腐蝕，等，可被防止。 —此外’ PE-CVD TMS Si02薄膜有和氮化矽薄膜相似的 挽f特徵，但是有低介電常數特徵，$是和氣化♦薄膜有 很的不同。結淪，如果PE-CVD TMS Si02薄膜被用來當503514 V. Description of the invention (34) The barrier edge film made of PE-CVD TMS SiO2 film used. By the way, as shown in the inspection results of the second embodiment, such as PE-CVD TMS Si02 film, there is a thin burst point similar to that of silicon nitride (siN). PE-CVD TMS SiO2 film is thick, has good water resistance, and has an excellent amount in the film. In conclusion, the corrosion of the lower conductive wiring 33 can be prevented without preventing water vapor penetration. In addition, if the lower barrier insulating film 32 is formed of a PE-CVD TMS SiO 2 film as in the present invention, the peripheral circuit portion of the lower conductive wiring 33 can be formed by the PE-CVD TMS SiO 2 film. protection. Therefore, the corrosion of the lower conductive wiring 33 can be prevented without preventing moisture from permeating through all the portions of the lower conductive wiring 33. Further, the upper surface of the porous insulating film 35 having a low dielectric constant is formed by a barrier film 34 formed by a PE-CVD TMS SiO 2 film and a protective layer 36 formed by a PE-CVD TMS SiO 2 film. Protected. In conclusion, the penetration of foreign water vapor into the porous insulating film 35 can be prevented. Therefore, the dielectric constant which changes according to the amount of water vapor contained in the porous insulating film 35 can be suppressed. The water vapor contained in the insulating film 35 is present from the beginning, and the water vapor flowing out to the peripheral circuit portion can be prevented, and the corrosion of the lower conductive wiring 33, etc. can be prevented.-In addition, 'PE-CVD TMS Si02 film has similar characteristics to silicon nitride film, but has a low dielectric constant characteristic. $ Is very different from gasification. ♦ Thin film. If PE-CVD TMS Si02 film is used as

503514 五、發明說明（35) 作絕緣層間薄膜，則較低的介電常數可被 說，如果PE-CVD TMS Si〇2薄膜被用來當作、、持s。具體來 膜，以及保護多孔隙絕緣薄膜35的上^表面且隔絕▲緣薄 有包含他們的絕緣層間薄膜的低的介雷赍的保護層’所 在上述之第五實施例中，在含氧可被維持。 石夕基底31所形成的熱氧化薄膜’以使用；機含化 CVD法所形成的NSG薄膜、BPSG薄膜、#，被 絕緣薄膜32。但，如本發明之電漿CVD法所形 &quot;503514 V. Description of the invention (35) As an insulating interlayer film, a lower dielectric constant can be said. If a PE-CVD TMS SiO2 film is used as, and holds s. Specifically, a film, and a protective layer that protects the upper surface of the porous insulating film 35 and isolates it. The edge is thin with a low dielectric layer including their insulating interlayer film. In the fifth embodiment described above, the oxygen-containing Be maintained. The thermally oxidized thin film 'formed on the Shixi substrate 31 is used; the NSG thin film, the BPSG thin film, and the insulating thin film 32 formed by the organic chemical CVD method are used. However, as the plasma CVD method of the present invention &quot;

TMS Si02薄膜可被使用。 t-CVD (第六實施例） 第1 4 A與1 4 C圖係為如本發明第六實施例的半導體 以及半導體裝置之製造方法斷面視圖。 义 第1 4C圖係為如本發明第六實施例的半導體裝置斷面 視圖。 在此半導體裝置中，和第五實施例不同的地方是，接 觸孔37的邊牆是以本發明中ipE —CVD TMS Si02薄膜39a所 覆蓋，以及導致多孔隙絕緣薄膜35並沒有從接觸孔37之内 表面曝露出。 此情況下，如果PE-CVD TMS Si02薄膜所做成的邊牆 保護層39a被加入第13F圖中，多孔隙絕緣薄膜35可以由本 發明中之PE-CVD TMS Si02薄膜從外面而被完美地防護 著。所以，在第五實施例中所解釋關於水氣的輸入以及放 出的優點，能被更加強。 為了要植入上述結構，如第14A圖所示，本發明中之TMS Si02 film can be used. t-CVD (Sixth Embodiment) Figs. 14A and 14C are cross-sectional views of a method of manufacturing a semiconductor and a semiconductor device according to a sixth embodiment of the present invention. Fig. 14C is a sectional view of a semiconductor device according to a sixth embodiment of the present invention. In this semiconductor device, the difference from the fifth embodiment is that the side wall of the contact hole 37 is covered by the ipE-CVD TMS Si02 film 39a in the present invention, and the porous insulating film 35 is not removed from the contact hole 37. The inner surface is exposed. In this case, if the side wall protective layer 39a made of the PE-CVD TMS Si02 film is added to FIG. 13F, the porous insulating film 35 can be perfectly protected from the outside by the PE-CVD TMS Si02 film in the present invention. With. Therefore, the advantages explained in relation to the input and discharge of water and gas as explained in the fifth embodiment can be further enhanced. In order to implant the above structure, as shown in FIG. 14A, in the present invention,

2060-4201-PF;nivek.ptd 第40頁 503514 五、發明說明（36) PE_CVD TMS Si〇2薄膜被使用以及在保護層36上被形成， 也覆盍了接觸孔3 7 ’在第1 4 E圖所示之階段以後。然後， 如第14A圖所示，PE-CVD TMS Si〇2薄膜39&amp;被以非等'、向性 (anisotropic)蝕刻，來留下接觸孔37的邊牆2PE — cvd TMS Si〇2薄膜3 9a。然後，如第1 4C圖所示，由銅或鋁所做 成的上導電佈線3 8，經過傳導薄膜和下導電佈線3 3連接起 來。 和上述，雖然本發明已以較佳實施例揭露如上，雖然 並非用以限定本發明，認何熟習此技藝者，在不脫離本發 明之精神和範圍内，當可作些許更動與潤飾，因此本發明 之保護範圍當視後附之申請專利範圍所界定者為準。 (其他實施例） 舉例，如第15圖所示，只以PE-CVD TMS Si02薄膜所 形成的下置絕緣薄膜22或23是直接地在石夕基底21或31上所 形成的，但具有包括雙層之多層次結構的下置絕緣薄膜2 2 或23，是將BPSG薄膜或熱氧化薄膜61以及PE-CVD TMS Si02薄膜62依序從底部所形成的，或更多可形成。此情況 下，將PE-CVD TMS Si02薄膜排在最上層是非常重要的。 進一步，如第16圖所示，被中置在下導電佈線33以及 上導電佈線65之間的單一絕緣層間薄膜63，可在基底20C 上被形成。 此情況中，絕緣層間薄膜6 3是由含石夕絕緣薄膜所做 成。而且，經過開放部分6 4而連接的下導電佈線3 3以及上 導電佈線6 5被形成來在絕緣層間薄膜6 3中挖出洞。2060-4201-PF; nivek.ptd Page 40 503514 V. Description of the invention (36) PE_CVD TMS SiO 2 film is used and formed on the protective layer 36, and is also covered with contact holes 3 7 ' After the stage shown in Figure E. Then, as shown in FIG. 14A, the PE-CVD TMS Si02 film 39 &amp; is etched anisotropically, leaving an edge wall 2PE of the contact hole 37—the cvd TMS Si02 film 3 9a. Then, as shown in FIG. 14C, the upper conductive wiring 38 made of copper or aluminum is connected to the lower conductive wiring 3 3 through a conductive film. As mentioned above, although the present invention has been disclosed as above with preferred embodiments, although it is not intended to limit the present invention, anyone skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application. (Other embodiments) For example, as shown in FIG. 15, the lower insulating film 22 or 23 formed of only the PE-CVD TMS SiO 2 film is directly formed on the Shixi substrate 21 or 31, but includes The two-layer multi-layered lower insulating film 2 2 or 23 is formed by sequentially forming a BPSG film or a thermal oxidation film 61 and a PE-CVD TMS Si02 film 62 from the bottom, or more can be formed. In this case, it is important to arrange the PE-CVD TMS Si02 film on the top layer. Further, as shown in Fig. 16, a single insulating interlayer film 63 interposed between the lower conductive wiring 33 and the upper conductive wiring 65 can be formed on the substrate 20C. In this case, the insulating interlayer film 63 is made of a stone-containing insulating film. Further, a lower conductive wiring 33 and an upper conductive wiring 65 connected to each other via the open portion 64 are formed to dig holes in the insulating interlayer film 63.

2060-4201-PF;nivek.ptd 第41頁 503514 五、發明說明（37) 如上所述，如本發明，含矽絕緣薄膜在基底上形成。 如本發明中之含矽絕緣薄膜，具有波數2270-2350 cm-i範 圍的紅外線吸附強度的峰值，以及2· 25-2· 40 g/cm3範圍 的薄膜密度，以及3· 3-4· 3範圍的相對介電常數。 含矽絕緣薄膜是電漿化薄膜形成氣體所形成的，是任 何一個具有Si-Η鍵之烷氧基化合物（Alkoxyl compound) 群組中所選出的，以及含有Si-Η鍵之環氧矽氮烷 (Sil〇xane)和02，N20，N02，C02，C0 及1120 群組中任何一個 所選出的含氧氣體，反應而成的。 如本實驗，在上述紅外線吸附強度峰值的範圍以及上 述薄膜密度的範圍的含矽絕緣薄膜，是厚、有低相對介電 常數、以及低水氣量在薄膜中。以及上述方法所形成之該 薄膜是相同的。 ~ 所以，如果上述之含矽絕緣薄膜用來當作覆蓋導電佈 線的絕緣薄膜、或當作阻隔絕緣膜來夾層，由中置在上導 電佈線以及下導電佈線之間所組成之用來覆蓋導電佈線的 絕緣薄膜、用來覆蓋導電佈線的絕緣薄膜、或整個層間絕 緣薄膜的介電常數，可被降低，當防止導電佈線腐蝕以及 漏電流（Leakage current)增加的時候〇2060-4201-PF; nivek.ptd page 41 503514 5. Description of the invention (37) As mentioned above, as in the present invention, a silicon-containing insulating film is formed on a substrate. For example, the silicon-containing insulating film in the present invention has a peak of infrared absorption intensity in a wavenumber of 2270-2350 cm-i, a film density in a range of 2.25-2 · 40 g / cm3, and 3 · 3-4 · Relative dielectric constant in 3 ranges. The silicon-containing insulating film is formed by a plasma-forming film forming gas, and is selected from any group of Alkoxyl compounds having a Si-Η bond, and an epoxy silicon nitrogen containing a Si-Η bond. Siloxane and 02, N20, N02, C02, C0, and any selected oxygen-containing gas in the group, reacted. As in this experiment, the silicon-containing insulating film in the range of the peak of the infrared absorption intensity and the range of the film density described above is thick, has a low relative dielectric constant, and has a low water vapor content in the film. The thin film formed by the above method is the same. ~ So, if the above silicon-containing insulating film is used as an insulating film covering conductive wiring, or as a barrier film, it is sandwiched between the upper conductive wiring and the lower conductive wiring. The dielectric constant of the insulating film of the wiring, the insulating film used to cover the conductive wiring, or the entire interlayer insulating film can be reduced when preventing the conductive wiring from being corroded and increasing the leakage current.

Claims (1)

503514 --—901174Μ_1年1月又曰 條正本 六、申請專利範圍 ^~^~、 1 · 一種薄膜形成方法，包括下列步驟··準備形成氣 體，是任何一個具有Si—η鍵之烷氧基化合物（Alk〇xyi compound)群組中所選出的，以及含有“^鍵之環氧 烧（Siloxane)和Ο,鳴〇，N〇2，⑶2，⑶及M群組中任^ 個所選出的含氧氣體；以及形成含矽絕緣膜在基底° 電漿化薄膜形成氣體反應而成的。 -’以 2·如申請專利範圍第丨項所述之薄膜形成方法，复 至少含有％、％群組中任何一個所選出的加入ς 成氣體。 寻膜形 3·如申請專利範圍第丨項所述之薄膜形成方法，波 具有Si-Η鍵之烷氧基化合物（Alk〇xyl c〇mp〇und)是三、^ 基矽烷（Trimethoxysilane (TMS : SiH(〇CH3)3))。 T 虱 4··如申請專利範圍第1項所述之薄膜形3成3方法，复 具有Si-H鍵之環氧石夕氮烧（Sii〇xane)是4次甲基石夕氮^ (Tetramethylsiloxane ； TMDSO : ( CH3 )2h i s-O^S i Η (CH^ λ 所形成的。 3 )2) 5·如申請專利範圍第1項所述之薄膜形成方法，其 平行板式電極板，被用來當作產生電漿的方法，以及&amp; 一 薄膜被形成時，具有100 KHz至1 MHz頻率之高頻率二: 使用在基底被載入的地方上之電極板，以及具有1 MHz^破 率或更高之高頻率能源被使用在正對著基底被載入的地 上之電極板的電極板。 ^ 6· —種半導體裝置之製造方法，包括下列步驟： 基底’在導電佈線被形成的表面上；以及形成含矽絕緣薄503514 --- 901174M January, January 1st, original article 6. Scope of patent application ^ ~ ^ ~, 1. A method for forming a thin film, including the following steps: preparing to form a gas, which is any alkoxy group having a Si-η bond Selected from the Alkoxyi compound group, and any of the selected compounds from the group of Siloxane and O, Na, 0, No. 2, 3, 2 and 3 containing the "^" bond. Oxygen gas; and the formation of a silicon-containing insulating film at the substrate ° plasma-forming thin film forming gas reaction.-'With the method of forming a thin film as described in item 1 of the scope of the patent application, which contains at least%,% group The gas to be added is selected by any one of them. Finding the film shape 3. According to the method for forming a thin film described in item 丨 of the patent application, an alkoxy compound having an Si-Η bond (Alk〇xyl c〇mp〇und) ) Is a trimethoxysilane (TMS: SiH (〇CH3) 3). T lice 4. · The method of forming a thin film into 3 as described in item 1 of the scope of patent application, which has a Si-H bond Epoxidite (SiiOxane) is a tetramethylsiloxane (Tetramethylsiloxane; TM DSO: (CH3) 2h i sO ^ S i Η (formed by CH ^ λ. 3) 2) 5 · As described in the patent application No. 1 of the thin film formation method, the parallel plate electrode plate is used as As a method for generating plasma, and &amp; a film having a high frequency of 100 KHz to 1 MHz when a film is formed, an electrode plate on a place where a substrate is loaded, and a breakage rate of 1 MHz or more A high-frequency and high-frequency energy source is used on an electrode plate facing an electrode plate on the ground where the substrate is loaded. ^ 6 · —A method for manufacturing a semiconductor device including the following steps: The substrate is on a surface on which conductive wiring is formed; And the formation of silicon-containing insulation 2060-4201-PFl;nivek.ptc 第43頁 503514 —--tE 901174U q/缶^月及日 修去_ 六、申請專利範圍 &quot; &quot; ^ ~*— 膜，用來覆蓋導電佈線，以電漿化薄膜形成氣體，其中薄 膜形成氣體，是任何一個具有Si_H鍵之烷氧基化合物彳 (Alkoxyl compound)群組中所選出的，以及含有Si〜H鍵之 環氧石夕氮烧（Siloxane)和〇队〇，n〇2，C02，（：0及1|2〇群細 中任何一個所選出的。 2群組 7 ·如申請專利範圍第6項所述之半導體裝置之製造方 法，其中含矽絕緣薄膜，用來覆蓋導電佈線，是保護層。 8·如申請專利範圍第7項所述之半導體裝置之製造方 法，進一步包括下列步驟：形成一層間絕緣薄膜，薄膜厚 度比保護層的厚，在保護層上，在形成保護層之後，用來 覆盖導電佈線。 9· 一種半導體裝置，其中含矽絕緣薄膜，具有波數 2270-2350 cnr1範圍的紅外線吸附強度的峰值，以及 2· 25-2. 40 g/cm3範圍的薄膜密度，以及3· 3-4· 3範圍的相 對介電常數’在基底上形成。 I 0 ·如申請專利範圍第9項所述之半導體裝置，進一步 包括：導電佈線，在基底表面上形成，其中含石夕絕緣薄 膜’覆蓋著導電佈線，用來接觸導電佈線。 II ·如申請專利範圍第9項所述之半導體裝置，進一步 包括：導電佈線；含矽絕緣薄膜，覆蓋著導電佈線，用來 接觸導電佈線，在基底表面上形成；以及保護層，·由含石夕 絕緣薄膜所做成，在絕緣薄膜上形成。 12·如申請專利範圍第9項所述之半導體裝置，進一步 包括：導電佈線’在基底表面上形成；下保護層，覆蓋著2060-4201-PFl; nivek.ptc page 43 503514 --- tE 901174U q / 缶 ^ month and day repair _ Sixth, the scope of patent application &quot; &quot; ^ ~ * — film, used to cover conductive wiring, to Plasma-forming film-forming gas, wherein the film-forming gas is selected from any group of Alkoxyl compounds with Si_H bonds, and epoxy sintered silicon oxide containing Si ~ H bonds (Siloxane) ) And 〇 team 〇, 〇2, C02, (: 0 and 1 | 20 group selected by any one of the group. 2 group 7 · The method of manufacturing a semiconductor device as described in item 6 of the scope of patent application, The silicon-containing insulating film is used to cover the conductive wiring and is a protective layer. 8. The method for manufacturing a semiconductor device as described in item 7 of the scope of patent application, further comprising the following steps: forming an interlayer insulating film with a film thickness greater than that of the protective layer The thickness of the protective layer is used to cover the conductive wiring after the protective layer is formed. 9 · A semiconductor device in which a silicon-containing insulating film has a peak of infrared absorption intensity in the wave number range of 2270-2350 cnr1, and 2 · 25-2. 40 A film density in the g / cm3 range and a relative dielectric constant in the range of 3 · 3-4 · 3 are formed on the substrate. I 0 · The semiconductor device according to item 9 of the scope of patent application, further comprising: conductive wiring, It is formed on the surface of the substrate, and the insulating film containing Shi Xi is covered with conductive wiring for contacting the conductive wiring. II. The semiconductor device according to item 9 of the scope of patent application, further comprising: a conductive wiring; a silicon-containing insulating film, Covered with conductive wiring for contacting conductive wiring and formed on the surface of the substrate; and a protective layer, made of an insulating film containing stone and formed on the insulating film. 12 · As described in item 9 of the scope of patent application The semiconductor device further includes: a conductive wiring is formed on a substrate surface; and a lower protective layer is covered with 2060-4201-PFl;nivek.ptc 第44頁 503514 ____案號 901174U 叫 --- 六、申請專利範圍 導電佈線’用來接觸導電佈線；主要絕緣薄膜’層疊在下 保護層上，用來接觸下保護層；以及上保護層，層疊在主 要絕緣薄膜上，用來接觸主要絕緣薄膜，其中下保護層以 及上保護層，是含矽絕緣薄膜所做成。 1 3 ·如申請專利範圍第1 2項所述之半導體裝置’其中 主要纟巴緣薄膜，是任何一個且有$ i 〇 F薄膜以及多孔絕緣薄 膜群組中所選出所做成的。 1 4·如申請專科範圍第9項所述之半導體裝置，進一步 包括：下導電佈線；上導電佈線；以及層間絕緣薄膜，中 置在下導電佈線以及上導電佈線之間，是在基底上形成’ 其中層間絕緣薄膜，是含矽絕緣薄膜所做成。 15·如申請專利範圍第14項所述之半導體裝置，其中 下導電佈線以及上導電佈線，是經過將層間絕緣薄膜穿過 所形成的開放部分而連接起來。 16·如申請專利範圍第9項所述之半導體裝置，進一步 包括： (i)下導電佈線，在基底表面上形成； (1 1 )上導電佈線；以及 (1 1 1 )層間絕緣薄膜，中置在下導電佈線以及上導 電佈線之間，層間絕緣薄膜包括： (a)下保護層，是覆蓋著下導電佈線，用來接觸下 導電佈線’的含矽絕緣薄膜所做成； 是層璺在下保護層上，用來接 (b )主要絕緣薄膜 觸下保護層；以及2060-4201-PFl; nivek.ptc Page 44 503514 ____Case No. 901174U Call --- 6. Patent application scope Conductive wiring is used to contact conductive wiring; the main insulating film is laminated on the lower protective layer and used to contact A protective layer; and an upper protective layer laminated on the main insulating film to contact the main insulating film, wherein the lower protective layer and the upper protective layer are made of a silicon-containing insulating film. 1 3 · The semiconductor device according to item 12 of the scope of the patent application, wherein the main thin film is any one selected from the group consisting of a thin film and a porous insulating film. 1 4. The semiconductor device according to item 9 of the scope of application, further comprising: a lower conductive wiring; an upper conductive wiring; and an interlayer insulating film, which is interposed between the lower conductive wiring and the upper conductive wiring and is formed on the substrate ' The interlayer insulating film is made of a silicon-containing insulating film. 15. The semiconductor device according to item 14 of the scope of patent application, wherein the lower conductive wiring and the upper conductive wiring are connected by passing an interlayer insulating film through an open portion formed. 16. The semiconductor device according to item 9 of the scope of patent application, further comprising: (i) a lower conductive wiring formed on the surface of the substrate; (1 1) an upper conductive wiring; and (1 1 1) an interlayer insulating film, medium It is placed between the lower conductive wiring and the upper conductive wiring. The interlayer insulating film includes: (a) a lower protective layer, which is a silicon-containing insulating film covering the lower conductive wiring and used to contact the lower conductive wiring; On the protective layer, used to contact (b) the main insulating film to contact the protective layer; and 2060-4201-PFl;nivek.ptc 第45頁 503514 修正 案號 90117414 六、申請專利範圍 (c )上保護層，是層疊在主要絕緣薄膜上，用來接 觸主要絕緣薄膜，的含矽絕緣薄膜所做成，其中下保護層 以及上保護層，是含矽絕緣薄膜所做成。 1 7.如申請專利範圍第1 6項所述之半導體裝置，其中 主要絕緣薄膜，是任何一個具有S i 0F薄膜以及多孔絕緣薄 膜群組中所選出所做成的。 1 8.如申請專利範圍第1 6項所述之半導體裝置，進一 步包括：開放部分，將層間絕緣薄膜穿過所形成的；以及 邊牆保護層，含矽絕緣薄膜所做成，在開放部分的邊牆上 形成的，其中下導電佈線以及上導電佈線，是經過開放部 分而連接起來。2060-4201-PFl; nivek.ptc Page 45 503514 Amendment No. 90117414 6. The scope of patent application (c) The protective layer is a silicon insulating film laminated on the main insulating film and used to contact the main insulating film. The lower protective layer and the upper protective layer are made of a silicon-containing insulating film. 1 7. The semiconductor device according to item 16 of the scope of patent application, wherein the main insulating film is selected from any group having a Si 0F film and a porous insulating film group. 18. The semiconductor device according to item 16 of the scope of patent application, further comprising: an open portion formed by passing an interlayer insulating film therethrough; and a side wall protective layer made of a silicon-containing insulating film in the open portion The lower conductive wiring and the upper conductive wiring are formed through the open part and connected. 2060-4201-PFl;nivek.ptc 第46頁 503514 第90117414號中文圖式修正頁 修正日期：91.7.8 P=0洚3桊婵 (相昏帘tw 30 60 80 ^vBeaf3(H) 120 150 180 〇2060-4201-PFl; nivek.ptc Page 46 503514 No. 90117414 Chinese Schematic Correction Page Revision Date: 91.7.8 P = 0 桊 婵 3 桊 婵 (Phase tw 30 60 80 ^ vBeaf3 (H) 120 150 180 〇 cooker M Mllt 503514 修止 補充 銅與碎濃度(cm'3)cooker M Mllt 503514 repair repair copper and broken concentration (cm'3) 第1〇圖Figure 10
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